Isocyanates and aromatic hydroxy compounds

ABSTRACT

An object of the present invention is to provide a process for producing isocyanates, which are industrially useful compounds, without using phosgene, and to provide a process for chemically recycling waste polycarbonate resin. The present invention discloses a process enabling isocyanate compounds to be produced without using phosgene as a raw material by subjecting a carbamic acid ester compound obtained by a reaction between an aromatic polycarbonate resin and an amine compound to a thermal decomposition reaction, while at the same time disclosing a process enabling chemical recycling of aromatic polycarbonate resin by recovering a divalent aromatic hydroxy compound forming aromatic polycarbonates.

RELATED APPLICATIONS

This application is a Divisional Application of U.S. application Ser.No. 12/743,767, filed May 19, 2010, now U.S. Pat. No. 7,977,504 which isa U.S. National Phase Application of International Application No.PCT/JP2008/070765, filed Nov. 14, 2008, which claims the benefit ofJapanese Patent Application No. 2007-299703, filed Nov. 19, 2007,Japanese Patent Application No. 2007-299497, filed Nov. 19, 2007, andJapanese Patent Application No. 2007-299504, filed Nov. 19, 2007, all ofwhich are herein incorporated by reference in their entireties.

TECHNICAL FIELD

The present invention relates to a process for producing isocyanatecompounds and aromatic hydroxy compounds, which are useful for rawmaterials for aromatic polycarbonate.

BACKGROUND ART

Plastics are used as product materials in all fields of daily life, andthe amount of plastics used is increasing each year. Accompanying thisincrease, the amount of discarded plastics is also extremely large, thusresulting in the treatment of plastics becoming a significant socialissue.

At present, the majority of plastic products are simply disposed of bybeing incinerated or buried following completion of their use. However,when waste plastic having high heat of combustion in terms of caloriesis disposed of by incinerating in an ordinary refuse incinerator,abnormal combustion occurs resulting in the problem of damage to theincinerator furnace. In addition, not only does this manner of disposalresult in wasted resources, but it also causes environmental problems interms of environmental contamination and discharge of carbon dioxidegas. Thus, it is extremely important to recycle waste plastics from theviewpoint of the formation of a recycling society as well.

Methods used to recycle waste plastics include material recycling, inwhich waste plastics are reused as is, chemical recycling, in whichwaste plastics are chemically degraded followed by recovery of monomersand other useful chemical raw materials, and thermal recycling, in whichthermal energy is recovered from waste plastics. Among these, sincematerial recycling is accompanied by heat treatment of the wasteplastics, the heat treatment has a considerable effect on both thechemical properties and physical properties of the waste plastics, andfrequently results in problems such as deterioration of impactresistance, deformation under a load or high temperatures, tensilestrength, bending strength, fluidity and other properties. In addition,although thermal recycling offers the advantage of being able to inhibitthe amount of fossil fuels used as a result of effectively utilizingthermal energy, there are also numerous problems such as damage to theincinerator furnace, discharge of carbon dioxide gas and the need toimplement measures against dioxins as described above.

Aromatic polycarbonate resins constitute a typical engineering plastichaving superior transparency, optical properties and mechanicalproperties, and are extremely high added value materials used in a widerange of applications such as CDs, DVDs and other optical fields,various home appliances, cameras, cell phones, OA equipment, medicalequipment, automobiles and other industrial fields, sports and otherrecreational fields, and roofing materials, alternative glass materialsand other construction fields.

Various methods have been proposed thus far for chemically recyclingaromatic polycarbonates.

According to Non-patent document 1, although a process is described forobtaining bisphenol A by chemically decomposing polycarbonate resin withammonia water, decomposition of the polycarbonate resin requires a longperiod of time, thereby resulting in the problem of being unsuitable forlarge-volume processing of waste plastics.

In addition, Patent document 1 discloses a process for recoveringbisphenol A by decomposing polycarbonate resin by adding ammonia waterand an organic solvent in the form of aluminum chloride to apolycarbonate resin. However, there are many cases in which chemicaldecomposition of the polycarbonate requires a long period of time withthis process as well.

Examples of processes for shortening the time required to decomposepolycarbonate resins in this manner may include a process for recoveringuseful materials from waste plastics having polycarbonate resin for themain component thereof disclosed in Patent document 2 which comprises astep of chemically decomposing a polycarbonate resin in a solutioncontaining waste plastic and a decomposition agent in the form of aprimary amine, and a step of recovering the decomposition product in theform of a useful material. In this process, the polycarbonate resin isreacted with an excess of primary amine equivalent to six or more timesthe number of moles of carbonic acid ester groups as calculated from themolecular weight of the repetitive units of the polycarbonate resin,followed by recovery of useful materials such as the degradation productin the form of bisphenol A and urea derivatives. In addition, accordingto Non-patent document 2, it is described that bisphenol A and1,3-dimethyl-2-imidazolidinone (DMI) are obtained by decomposingpolycarbonate with N,N′-dimethyl-1,2-diaminoethane. Among these recoveryproducts, although bisphenol A can be easily imagined to be used as araw material for the production of polycarbonate resin, there are nodescriptions regarding the use of urea derivatives or DMI, and theusefulness thereof is unclear.

In addition, according to Patent document 3, for example, a process isdisclosed for obtaining bisphenols and diaryl carbonate by cleavingpolycarbonate resin by carrying out a transesterification reactionbetween polycarbonate resin and phenol in the presence of a catalyst. Itis described to the effect that monomers obtained by this process can berecondensed to produce polymer plastics. In addition, in Patent document4, for example, a process for recovering useful materials from wasteplastics mainly composed of polycarbonate is disclosed wherebydecomposition products are recovered in the form of useful materials bychemically decomposing polycarbonate resin in a solution containing anorganic solvent that causes polycarbonate resin to dissolve or swell, atertiary amine and a lower alcohol. In this process, examples ofrecovered useful materials are listed as being bisphenol A and carbonicacid ester. Since each of these processes requires an alkaline catalystto decompose the polycarbonate by a transesterification reaction, thereare many cases in which the procedure becomes complex, such as requiringdeactivation of the alkaline catalyst during separation and purificationof the decomposition products.

As an example of a process not requiring a catalyst, Non-patent document3 discloses a process for producing bisphenol A by hydrolyzingpolycarbonate under supercritical conditions (supercritical aqueous orsubcritical aqueous conditions). Although there is no descriptionregarding yield and the reaction efficiency is not clearly stated inthis document, since the reaction is carried out under high temperatureand high pressure conditions, not only is there the possibility of theconcurrent occurrence of thermal decomposition of the bisphenol A undersuch conditions, but also due to the extremely strong acidity of thewater itself under supercritical aqueous conditions along with the hightemperature in excess of 300° C. and high pressure in excess of 200 atm,the apparatus and equipment become excessively complex, thereby makingit difficult to carry out the process economically.

Patent document 5 discloses a process for recovering aromatic bisphenoland carbonic acid ester formed by reacting polycarbonate obtained bymelting and filtration from disk-shaped optical recording media with analiphatic alcohol having 1 to 6 carbon atoms in a subcritical orsupercritical state. In this process, in addition to the reaction vesselbeing large since an excess of aliphatic alcohol is used based on thepolycarbonate, similar to the case of the process described inNon-patent document 3, since the reaction vessel is required to be of adesign capable of withstanding a high temperature and high pressurestate, the large reactors used in typical commercial plants encounterdifficulties both in terms of design and economy.

Although polycarbonates have a typical structure in which, for example,a bisphenol A unit and a carbonyl unit are alternately arranged in apolymer chain, the chemical recycling processes disclosed thus fardisclose technologies that only attempt to effectively recycle one ofthese units or technologies that only attempt to recover the bisphenolA. However, there have been no successful examples of chemicallyrecycling both units in the form of effective compounds at a highrecovery yield.

Thus, although there has been a strong desire for the development of aprocess for chemically recycling waste aromatic polycarbonate resins, aneffective process has yet to be found.

As previously described, polycarbonate resins are formed from, forexample, bisphenol A and carbonyl units. The recovery of this carbonylunit in the form of an industrially effective compound is an importantissue for chemical recycling of polycarbonate resins. Examples ofindustrially effective compounds having a carbonyl group may includecarbonic acid esters and isocyanates. Isocyanates are widely used asproduction raw materials of polyurethane foam, paints and adhesives. Themost commonly used process for industrial production of isocyanatesconsists of reacting an amine compound with phosgene (phosgene method),and nearly the entire amount of isocyanates produced throughout theworld are produced according to the phosgene method. However, thephosgene method has numerous problems.

Firstly, this method requires the use of a large amount of phosgene asraw material. Phosgene is extremely toxic and requires special handlingprecautions to prevent exposure of handlers thereof, and also requiresspecial apparatuses to detoxify waste.

Secondly, since highly corrosive hydrogen chloride is produced in largeamounts as a by-product of the phosgene method, in addition to requiringa process for detoxifying the hydrogen chloride, in many caseshydrolytic chlorine is contained in the isocyanates produced, which mayhave a detrimental effect on the weather resistance and heat resistanceof polyurethane products in the case of using isocyanates produced usingthe phosgene method.

On the basis of this background, a process for producing isocyanates hasbeen sought that does not use phosgene. One example of a method forproducing isocyanate compounds without using phosgene that has beenproposed involves thermal decomposition of carbamic acid esters.Isocyanates and hydroxy compounds have long been known to be obtained bythermal decomposition of carbamic acid esters (see, for example,Non-patent document 4). The basic reaction is illustrated by thefollowing formula:R(NHCOOR′)_(a)→R(NCO)_(a) +aR′OH  (1)(wherein R represents an organic residue having a valence of a, R′represents a monovalent organic residue, and a represents an integer of1 or more).

Among carbamic acid esters, aryl carbamates, in which the ester group isan aromatic group, offer the advantage of allowing the setting of alower temperature for the thermal decomposition reaction as comparedwith alkyl carbamates in which the ester group is an alkyl group (see,for example, Patent document 6).

Various processes have been disclosed thus far as processes forproducing aryl carbamates. Patent document 7 describes the obtaining ofa corresponding alkyl aryl monocarbamate at a yield of 90 to 95% byreacting an alkyl monoamine and a diaryl carbonate in the presence of asolvent such as benzene, dioxane or carbon tetrachloride. In addition,Patent document 8 proposes a process for continuously producing methylcarbamic acid phenyl ester from methylamine and diphenyl carbonate.

However, each of these processes produces alkyl aryl carbamate using alower alkyl monoamine for the amine, and do not constitute a process forproducing an alkyl aryl polycarbamate. In the case of producing acorresponding alkyl polycarbamic acid aryl ester from an alkyl polyaminesuch as alkyl diamine or alkyl triamine, there are difficult problemsthat are completely different from those in the case of using an alkylmonoamine. This is because, although only urea compounds are produced asby-products due to side reactions represented by formula (3) and/orformula (4) in addition to the reaction represented by formula (2) inthe case of an alkyl monoamine, in the case of an alkyl polyamine suchas alkyl diamine or alkyl triamine, an extremely large number of typesof urea compounds are produced as by-products, such as the compoundsrepresented by formula (5) and/or formula (6) and/or formula (7).

(wherein R′ represents a monovalent alkyl group or aromatic group, Arrepresents a monovalent aromatic group, and p, q and r respectivelyrepresent an integer of 1 or more.)

Namely, there are the problems of these various urea compound sidereactions causing a decrease in the yield of the target compound in theform of the alkyl aryl polycarbamate, as well as the extreme difficultyin separating and purifying the target product from a mixture of theseurea compounds and polyurea compounds.

Although Patent document 9 describes a process for synthesizing anaromatic urethane by reacting an aromatic amine and a diaryl carbonatein the presence of a Lewis acid catalyst at a temperature of 140 to 230°C., in this process as well, the use of a Lewis acid results in theproblem of corrosion of the apparatus as well as difficulty inseparating and recovering the product.

Patent document 10 discloses a process for producing alkyl arylpolycarbamate comprising the use of 1 to 3 equivalents of diarylcarbonate based on 1 equivalent of amino group of alkyl polyamine, usingan aromatic hydroxy compound for the reaction solvent, and carrying outthe reaction in the state of a substantially homogeneous solution whenproducing alkyl polycarbamic acid aryl ester by reacting alkyl polyamineand diaryl carbonate. According to this patent document, alkylpolycarbamic acid aryl ester is obtained with high selectivity and at ahigh yield of normally 96% or more and 98% or more in preferableembodiments thereof. However, since the formation of urea compounds hasbeen confirmed, although in very small amounts, this process is unableto completely avoid the formation of urea compounds.

On the other hand, thermal decomposition of carbamic acid esters issusceptible to the simultaneous occurrence of various irreversible sidereactions such as thermal denaturation reactions undesirable forcarbamic acid esters or condensation of isocyanates formed by thethermal decomposition. Examples of these side reactions may include areaction in which urea bonds are formed as represented by the followingformula (8), a reaction in which carbodiimides are formed as representedby the following formula (9), and a reaction in which isocyanurates areformed as represented by the following formula (10) (see, Non-patentdocument 4 and Non-patent document 5).

(wherein R and R′ independently represent monovalent alkyl groups oraromatic groups.)

In addition to these side reactions leading to a decrease in yield andselectivity of the target isocyanate, in the production ofpolyisocyanates in particular, these reactions may make long-termoperation difficult as a result of, for example, causing theprecipitation of polymeric solids that clog the reaction vessel.

Various processes have been proposed thus far for producing isocyanatesusing a carbamic acid ester for the raw material.

According to Patent document 11, an aromatic diisocyanate and/orpolyisocyanate is produced by going through the following two steps.More specifically, in the first step, an aromatic primary amine and/oran aromatic primary polyamine is reacted with an O-alkyl carbamate inthe presence or absence of a catalyst and in the presence or absence ofurea and alcohol to form an aryl diurethane and/or aryl polyurethanefollowed by removal of the ammonia formed as necessary. In the secondstep, an aromatic isocyanate and/or aromatic polyisocyanate are obtainedby thermal decomposition of the aryl diurethane and/or arylpolyurethane.

There are several known methods for forming a corresponding isocyanateand alcohol by thermal decomposition of a (cyclic) aliphatic, andparticularly an aromatic, monourethane and diurethane, including methodscarried out in the gaseous phase at a high temperature, and methodscarried out in a liquid phase under comparatively low temperatureconditions. In these methods, however, the reaction mixture gives riseto the side reactions described above, thereby causing, for example, theformation of sediment, polymeric substances and obstructions in thereaction vessel and recovery apparatus, or the formation of substancesthat adhere to the sidewalls of the reaction vessel, thereby resultingin poor economic efficiency in the case of producing isocyanates over along period of time.

Thus, the use of a chemical method, such as the use of a specialcatalyst (see, for example, Patent document 12 and Patent document 13)or a catalyst combined with an inert solvent (see, for example, Patentdocument 14), has been disclosed to improve the yield in the thermaldecomposition of urethane.

More specifically, Patent document 15 describes a process for producinghexamethylene diisocyanate consisting of thermal decomposition ofhexamethylene diethyl urethane in the presence of dibenzyl toluene usedas a catalyst and in the presence of a catalyst mixture composed ofmethyl toluene sulfonate and diphenyl tin dichloride. However, sincethere are no detailed descriptions of production or isolation of thestarting components or purification and arbitrary recovery of thesolvent and catalyst mixture, the economic efficiency of this processcould not be evaluated.

According to the method described in Patent document 16, urethane can beeasily broken down into isocyanate and alcohol in a carbon-containingfluidized bed without using a catalyst. In addition, according to thedescription of Patent document 17, hexamethylene dialkyl urethane can bedecomposed in the gaseous phase at a temperature in excess of 300° C. inthe presence or absence of a gas permeable packaging material made of,for example, carbon, copper, brass, steel, zinc, aluminum, titanium,chromium, cobalt or quartz to form hexamethylene diisocyanate. Accordingto the description of Patent document 16, this method is carried out inthe presence of a hydrogen halide and/or hydrogen halide donor. However,this method is unable to achieve a yield of hexamethylene diisocyanateof 90% or more. This is because the decomposition products are partiallyrecombined resulting in the formation of urethane bonds. Thus, thehexamethylene diisocyanate is required to be additionally purified bydistillation, which frequently increases yield loss.

Moreover, according to the description of Patent document 18, amonocarbamate is disclosed to be able to be decomposed with favorableyield without using a solvent and in the presence or absence of acatalyst and/or stabilizer at a comparatively low temperature andadvantageously under a reduced pressure. The decomposition products(monoisocyanate and alcohol) are removed from a boiling reaction mixtureby distillation and separately captured by separative condensation. Amethod for removing by-products formed during thermal decompositionconsisting of partially removing the reaction mixture outside the systemis described in a generic form. Thus, although by-products can beremoved from the bottom of the reaction vessel, problems remain withrespect to the case of adherence to the sidewalls of the reaction vesselas previously described, and problems with respect to long-termoperation remain unsolved. In addition, there is no descriptionregarding industrial utilization of the removed reaction mixture(containing large amounts of useful components).

According to the description of Patent document 19, thermaldecomposition of an aliphatic, alicyclic or aromatic polycarbamate iscarried out in the presence of an inert solvent at 150° C. to 350° C.and 0.001 to 20 bar, and in the presence or absence of a catalyst and anassistant in the form of hydrogen chloride, organic acid chloride,alkylation agent or organic tin chloride. By-products formed, can becontinuously removed from the reaction vessel together with the reactionsolution, for example, and a corresponding amount of fresh solvent orrecovered solvent is added simultaneously. A shortcoming of this methodis, for example, a reduction in the space-time yield of polyisocyanateas a result of using a refluxing solvent, while also requiringconsiderable energy, including that for recovery of the solvent.Moreover, the assistants used are volatile under the reactionconditions, resulting in the potential for contamination of thedecomposition products. In addition, the amount of residue is largebased on the formed polyisocyanate, thus leaving room for doubtregarding economic efficiency and the reliability of industrial methods.

According to the description of Patent document 20, a method isdescribed for continuous thermal decomposition of a carbamate such asthe alicyclic diurethane,5-(ethoxycarbonylamino)-1-(ethoxycarbonylaminomethyl)-1,3,3-trimethylcyclohexane,supplied along the inner surface of a tubular reactor in a liquid formin the presence of a high boiling point solvent. This method has theshortcomings of low yield during production of (cyclic) aliphaticdiisocyanates and low selectivity. In addition, there is no descriptionof a continuous method accompanying recovery of recombined or partiallydecomposed carbamates, while there is also no mention made ofpost-treatment of solvent containing the by-products and catalyst.

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DISCLOSURE OF INVENTION Problems to be Solved by the Invention

An object of the present invention is to provide a process for producingisocyanates, which are industrially useful compounds, without usingphosgene as described above, while at the same time providing a processfor chemically recycling waste aromatic polycarbonate resin.

Means for Solving the Problems

As a result of conducting extensive studies on the above-mentionedproblems, the inventors of the present invention found that theabove-mentioned problems can be solved by a process in which a carbamicacid ester compound obtained by a reaction between an aromaticpolycarbonate resin and a specific polyamine compound is subjected to athermal decomposition reaction, thereby leading to completion of thepresent invention.

Namely, in a first aspect of the present invention, there is provided:

[1] a process for producing a divalent aromatic hydroxy compound and anisocyanate compound, comprising the steps of:

reacting an aromatic polycarbonate resin and an amine compound having aprimary amino group to obtain a mixture containing a carbamic acid esterand a compound having an aromatic hydroxyl group, which are originatedfrom the aromatic polycarbonate; and

subjecting the carbamic acid ester to a thermal decomposition reactionto obtain the divalent aromatic hydroxy compound and the isocyanatecompound,

[2] the process according to item [1], wherein the reaction between thearomatic polycarbonate resin and the amine compound is carried out inthe presence of a monovalent aromatic hydroxy compound as a reactionsolvent,

[3] the process according to item [1] or [2], wherein the reactionbetween the aromatic polycarbonate resin and the amine compound iscarried out in the absence of a catalyst,

[4] the process according to any one of items [1] to [3], wherein thethermal decomposition reaction of the carbamic acid ester is carried outin the absence of a catalyst,

[5] the process according to any one of items [1] to [4], wherein areactor in which the reaction between the aromatic polycarbonate resinand the amine compound is carried out differs from a reactor used forthe thermal decomposition reaction of the carbamic acid ester,[6] the process according to item [5], further comprising transferringthe mixture containing the carbamic acid ester obtained by reacting thearomatic polycarbonate resin with the amine compound to the reactor usedfor the thermal decomposition reaction of the carbamic acid ester,[7] the process according to item [6], wherein the mixture containingthe carbamic acid ester is transferred while maintaining a temperaturewithin a range of from 10° C. to 180° C.,[8] the process according to any one of items [1] to [7], wherein a lowboiling point component formed in the thermal decomposition reaction ofthe carbamic acid ester is recovered from the reactor in a form of agaseous phase component, and a liquid phase component is recovered froma bottom of the reactor,[9] the process according to item [8], wherein the recovery of thegaseous phase component and the recovery of the liquid phase componentare carried out continuously,[10] the process according to item [8] or [9], wherein the low boilingpoint component is an isocyanate compound and/or a monovalent aromatichydroxy compound,[11] the process according to item [8] or [9], wherein the liquid phasecomponent contains a divalent aromatic hydroxy compound and/or carbamicacid ester,[12] the process according to any one of items [8] to [11], wherein theliquid phase component is recycled to a top of the reactor in which thethermal decomposition reaction is carried out,[13] the process according to any one of items [1] to [12], wherein thearomatic polycarbonate resin is a waste polycarbonate resin,[14] the process according to any one of items [1] to [13], wherein theamine compound is a compound represented by the following formula (11):

(wherein R¹ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms and aromatic groups having6 to 20 carbon atoms, the above groups contain an atom selected fromcarbon and oxygen atoms, and have an atomic number equal to n, and

n represents an integer of from 2 to 10),

[15] the process according to item [14], wherein the amine compound is adiamine compound in which n is 2 in formula (11),

[16] the process according to item [2], wherein a standard boiling pointof the monovalent aromatic hydroxy compound is lower than a standardboiling point of the divalent aromatic hydroxy compound,

[17] the process according to item [2] or [16], wherein the monovalentaromatic hydroxy compound is an aromatic hydroxy compound which isrepresented by the following formula (12) and which has at least onesubstituent R²:

(wherein ring A represents an aromatic hydrocarbon ring which has 6 to20 carbon atoms and which may have a substituent, and the ring A may bea monocyclic or heterocyclic ring, and

R² represents an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups contain an atom selected from thegroup consisting of carbon, oxygen and nitrogen atoms, and R² may alsobond with A to form a ring structure),

[18] the process according to item [17], wherein the monovalent aromatichydroxy compound has a structure in which the ring A contains at leastone structure selected from the group consisting of a benzene ring, anaphthalene ring and an anthracene ring.

In addition, in the second aspect of the present invention, there isprovided:

[19] a carbamic acid ester compound represented by the following formula(13):

(wherein R³ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms and aromatic groupscontaining 6 to 20 carbon atoms, the above groups contain an atomselected from carbon and oxygen atoms,

each of R⁴ and R⁵ independently represents a substituent selected fromthe group represented by the following formula (14):

and, each of x, y and z independently represents an integer of 0 ormore).

Advantageous Effects of the Invention

According to the present invention, in addition to being able toefficiently produce an isocyanate compound without using phosgene, adivalent aromatic hydroxy compound can be obtained by chemicallyrecycling an aromatic polycarbonate resin.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a conceptual drawing showing an apparatus forpreparing an aromatic polycarbonate-containing mixed liquid used in anexample of the of the present invention;

FIG. 2 illustrates a conceptual drawing showing an apparatus forproducing a carbamic acid ester used in an example of the presentinvention;

FIG. 3 illustrates a conceptual drawing showing an apparatus forproducing an isocyanate and aromatic hydroxy compound used in an exampleof the present invention;

FIG. 4 illustrates a conceptual drawing showing an apparatus forproducing an isocyanate and aromatic hydroxy compound used in an exampleof the present invention;

FIG. 5 illustrates a conceptual drawing showing an apparatus forproducing an isocyanate and aromatic hydroxy compound used in an exampleof the present invention;

FIG. 6 illustrates a conceptual drawing showing an apparatus forproducing an isocyanate and aromatic hydroxy compound used in an exampleof the present invention;

FIG. 7 illustrates a conceptual drawing showing an apparatus forproducing an isocyanate and aromatic hydroxy compound used in an exampleof the present invention;

FIG. 8 is a drawing of NMR analysis (¹H-NMR) of a mixture containing acarbamic acid ester compound indicated in Example 23 of the presentinvention; and

FIG. 9 is a drawing of NMR analysis (¹³C-NMR) of a mixture containing acarbamic acid ester compound indicated in Example 23 of the presentinvention.

DESCRIPTION OF REFERENCE NUMERICALS

-   (FIG. 1)-   100, 101, 103: storage tank, 102: reactor, 10, 11, 12: line-   (FIG. 2)-   103, 201, 203: storage tank, 202: reactor, 21, 22, 23: line-   (FIG. 3)-   203, 304, 308, 309, 311, 316, 317, 321, 322: storage tank,-   301: thin film distillation apparatus, 302, 312, 313, 318:    continuous multistage distillation column-   303, 308, 314, 319: condenser-   305, 310, 315, 320: reboiler-   31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47,    48, 49, 50, 51, 52: line-   (FIG. 4)-   203, 407, 404, 409, 411, 416, 417, 421, 422: storage tank-   401: thin film distillation apparatus, 402, 412, 413, 418:    continuous multistage distillation column-   403, 308, 414, 419: condensor, 405, 415, 420: reboiler-   60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76,    77, 78, 79, 80, 81, 82: line-   (FIG. 5)-   203, 504, 506, 507, 510, 512, 515, 517: storage tank-   501: thin film distillation apparatus, 502, 508, 513: continuous    multistage distillation column-   503, 509, 514: condenser, 505, 511, 516: reboiler-   A1, A2, A3, A4, A5, A6, A7, A8, A9, A10, A11, A12, A13, A14, A15,    A16, A17, A18, A19, A20, A21: line-   (FIG. 6)-   512, 603, 605, 608, 610: storage tank, 601, 606: continuous    multistage distillation column-   602, 607: condenser, 604, 609: reboiler-   B1, B2, B3, B4, B5, B6, B7, B8, B9, B10, B11, B12: line-   (FIG. 7)-   700, 701, 702, 714, 715: storage tank, 703: reactor-   704, 707, 710: continuous multistage distillation column, 705, 708,    711: condenser-   706, 709, 713: reboiler-   C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15,    C16, C17: line

BEST MODE FOR CARRYING OUT THE INVENTION

The following provides a detailed explanation of the best mode forcarrying out the present invention (to be referred to as “the presentembodiment”). Furthermore, the present invention is not limited to thefollowing present embodiment, but rather can be modified in various wayswithin the scope of the gist thereof.

The process of the present embodiment is a process for producing adivalent aromatic hydroxy compound and an isocyanate compound, whichcomprises the steps of: reacting an aromatic polycarbonate resin and anamine compound having primary amino groups to obtain a mixturecontaining a carbamic acid ester and a compound having an aromatichydroxyl group, which are originated from the aromatic polycarbonate;and subjecting the carbamic acid ester to a thermal decompositionreaction to obtain the divalent aromatic hydroxy compound and theisocyanate compound.

<Aromatic Polycarbonate>

An aromatic polycarbonate used in the present embodiment refers to apolymer having a carbonic acid ester of a divalent aromatic hydroxycompound as a repetitive unit thereof, and is represented by thefollowing formula (15):

(wherein Ar represents a divalent aromatic group having 6 to 20 carbonatoms, and k represents an integer of 0 or more).

There are no particular limitations on the Ar constituting the aromaticpolycarbonate, and is an aromatic group having the structure Ar(OH)₂, inwhich two hydroxyl groups are added to the Ar group, or in other words,an aromatic group in which two hydroxyl groups have been removed from adivalent aromatic hydroxy compound. Examples of the divalent aromatichydroxy compound represented by Ar(OH)₂ may preferably include adivalent aromatic hydroxy compound represented by the following formula(16):

(wherein X represents an alkylidene or cycloalkylidene, which has 1 to 8carbon atoms, S, SO₂, O, C═O or a single bond, R⁶ represents an alkylgroup having 1 to 5 carbon atoms, Cl or Br, and m represents an integerof 0 to 2).

Examples of such divalent aromatic hydroxy compounds may include4,4′-dihydroxydiphenyl, α,α′-bis-(4-hydroxyphenyl)-m-diisopropylbenzene,4,4′-dihydroxydiphenyl sulfide, 2,2-bis-(4-hydroxyphenyl)-propane,2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane,2,2-bis-(3,5-dichloro-4-hydroxyphenyl)-propane,2,2-bis-(3,5-dibromo-4-hydroxyphenyl)-propane,1,1-bis-(4-hydroxyphenyl)-cyclohexane and1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

Among these divalent aromatic hydroxy compounds, 4,4′-dihydroxyphenyl,α,α′-bis-(4-hydroxyphenyl)-m-diisopropylbenzene,2,2-bis-(4-hydroxyphenyl)-propane and1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane are preferable,2,2-bis-(4-hydroxyphenyl)-propane is more preferable.

The aromatic polycarbonate used in the present embodiment may also beproduced by any polymerization method. Although generally produced by amethod such as interfacial polymerization using phosgene or meltpolymerization using diphenyl carbonate, either method may be used andproduction is independent of the production method.

Although there are no particular limitations on the degree ofpolymerization of the aromatic polycarbonate provided it hasthermoplasticity, the weight average molecular weight is generallywithin a range of from 1,000 to 500,000, preferably within a range offrom 5,000 to 200,000, and more preferably within a range of from 10,000to 80,000. The weight average molecular weight of the aromaticpolycarbonate can be measured by gel permeation chromatography (solvent:tetrahydrofuran, standard: polystyrene).

The aromatic polycarbonate used in the present embodiment may also havea branched structure as a result of incorporating a multifunctionalbranching agent in the molecular chain thereof. Examples of branchingagents may include phloroglucinol,4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane,1,3,5-tri-(4-hydroxyphenylbenzene), 1,1,1-tri-(4-hydroxyphenyl)-ethane,tri-(4-hydroxyphenyl)-phenylmethane,2,2-bis-[4,4-bis-(4-hydroxyphenyl)-cyclohexyl]-propane,2,4-bis-(4-hydroxyphenyl-isopropyl)-phenol,2,6-bis-(2-hydroxy-5′-methyl-benzyl)-4-methylphenol,2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane,hexa-(4-(4-hydroxyphenyl-isopropyl)-phenyl)-orthophthalic acid ester,tetra-(4-hydroxyphenyl)-methane,tetra-(4-(4-hydroxyphenyl-isopropyl)-phenoxy-methane, isatin-bis-cresol,pentaerythritol, 2,4-dihydroxybenzoic acid, trimesic acid, cyanuricacid, 1,4-bis-((4′,4″-dihydroxytriphenyl)-methyl)-benzene,α,α′,α″-tris-(4-hydroxyphenyl)-1,3,4-triisopropenyl benzene and thelike.

In addition, there are cases in which the aromatic polycarbonatecontains a chain terminator and/or a group originated from a chainterminator following the use of a chain terminator such as phenol,octylphenol (including isomers), cumylphenol (including isomers) orbutylphenol (including isomers) during production thereof, and even sucharomatic polycarbonates can be used in the process of the presentembodiment without any problems whatsoever.

Although aromatic polycarbonates are generally used in lenses, compactdisks, construction materials, automobile parts, chasses of OA equipmentand camera bodies and the like, aromatic polycarbonates that have becomewaste following completion of use can also be used in the presentembodiment. In addition, aromatic polycarbonates in the form of, forexample, waste generated during the production of moldings, cuttings ormoldings no longer able to be used, defective moldings or aromaticpolycarbonates used to clean molding machines can also be used in thepresent embodiment. Thus, aromatic polycarbonates may contain commonlyused known additives such as mineral fillers such as quartz powder,glass powder, glass fibers, stabilizers, UV protectants, lubricants,pigments or dyes, as well as polymeric blended components using as rawmaterials thereof styrene, acrylonitrile or butadiene and the like. Insuch cases, these aromatic polycarbonates may be used as is in a stateof being contained within a range that does not impair the essence ofthe present embodiment, or these aromatic polycarbonates may be usedfollowing the removal of such additives or blended components bysuitable methods. Known methods can be used to remove these additivesand the like, examples of which may include methods such as filtration,membrane separation, centrifugal separation, precipitation, distillativeseparation or crystallization in a state of an aromatic polycarbonatemelt or, for example, a solution containing a solvent to be describedlater and the aromatic polycarbonate, and methods using adsorptiveseparation using, for example, activated charcoal, diatomaceous earth,cellulose or zeolite.

The aromatic polycarbonate used in the present embodiment is preferablyused in a state of being granulated or crushed to a suitable size. Fromthe viewpoint of allowing the reaction with the polyamine compound toproceed rapidly, the mean dimension is preferably 10 mm or less, andfrom the viewpoints of ease of granulation or crushing and handlingease, preferably 0.5 mm or more. Namely, the mean dimension ispreferably from 0.1 to 10 mm and more preferably from 0.5 to 5 mm.

<Amine Compound>

An amine compound represented by the following formula (17) is used forthe amine compound having primary amino groups used in the presentembodiment:

(wherein R¹ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms and aromatic groups having6 to 20 carbon atoms, the above groups contain an atom selected fromcarbon and oxygen atoms, and have an atomic number equal to n, and nrepresents an integer of 2 to 10).

In formula (17) above, a polyamine compound in which n is 2 or more isused preferably, and a diamine compound in which n is 2 is used morepreferably.

Examples of R¹ in formula (17) above may include alkyl groups having 1to 20 carbon atoms and cycloalkyl groups having 5 to 20 carbon atoms,and examples of such R¹ groups may include linear hydrocarbon groupssuch as a methylene, dimethylene, trimethylene, tetramethylene,pentamethylene, hexamethylene or octamethylene group; unsubstitutedalicyclic hydrocarbon groups such as a cyclopentane, cyclohexane,cycloheptane, cyclooctane or bis(cyclohexyl)alkane; alkyl-substitutedcyclohexanes such as methylcyclopentane, ethylcyclopentane,methylcyclohexane (including isomers), ethylcyclohexane (includingisomers), propylcyclohexane (including isomers), butylcyclohexane(including isomers), pentylcyclohexane (including isomers) orhexylcyclohexane (including isomers); dialkyl-substituted cyclohexanessuch as dimethylcyclohexane (including isomers), diethylcyclohexane(including isomers) or dibutylcyclohexane (including isomers);trialkyl-substituted cyclohexanes such as 1,5,5-trimethylcyclohexane,1,5,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (includingisomers) or 1,5,5-tributylcyclohexane (including isomers);monoalkyl-substituted benzenes such as toluene, ethylbenzene orpropylbenzene; dialkyl-substituted benzenes such as xylene,diethylbenzene or dipropylbenzene; and aromatic hydrocarbons such asdiphenylalkane or benzene. Among these, groups such as hexamethylene,phenylene, diphenylmethane, toluene, cyclohexane, xylenyl,methylcyclohexane, isophorone and dicyclohexylmethane are usedpreferably.

Examples of such amine compounds may include aliphatic diamines such ashexamethylene diamine, 4,4′-methylenebis(cyclohexylamine) (includingisomers), cyclohexane diamine (including isomers) or3-aminomethyl-3,5,5-trimethylcyclohexylamine (including isomers); andaromatic diamines such as phenylene diamine (including isomers), toluenediamine (including isomers) or 4,4′-methylene dianiline. Among these,aliphatic diamines such as hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) (including isomers), cyclohexanediamine (including isomers) or3-aminomethyl-3,5,5-trimethylcyclohexylamine (including isomers) areused preferably, hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) and3-aminomethyl-3,5,5-trimethylcyclohexylamine are used more preferably.

<Reaction of Aromatic Polycarbonate and Amine Compound Having PrimaryAmino Groups>

Next, an explanation is provided of the reaction between an aromaticpolycarbonate and an amine compound having primary amino groups in thepresent embodiment.

Although varying according to the reacted compounds, the reactionconditions under which the reaction between the aromatic polycarbonateand the amine compound having primary amino groups is carried out aresuch that the stiochiometric ratio of the amino groups of the aminecompound to the carbonate bonds that comprises the aromaticpolycarbonate is preferably within a range of from 0.0001 to 2. Thisstoichiometric ratio is preferably 1 or less, more preferably 0.5 orless and even more preferably 0.2 or less in order to reduce ureacompound by-products and enhance the yield of the target compound in theform of carbamic acid ester. In addition, although it is preferable thatthe amino groups of the amine compound be as few as possible withrespect to carbonate bonds constituting the aromatic polycarbonate inorder to increase the reaction rate and allow the reaction to rapidly becompleted, in consideration of the size of the reactor, thestiochiometric ratio is more preferably 0.001 or more and even morepreferably 0.01 or more.

The reaction temperature is generally within a range of from 0 to 300°C. Although a high temperature is preferable in order to increase thereaction rate, since undesirable reactions may occur at hightemperatures, the reaction temperature is preferably within a range offrom 10° C. to 250° C. and more preferably within a range of from 20° C.to 200° C. A known cooling apparatus or heating apparatus may beinstalled in the reactor used to carry out the reaction in order tomaintain a constant reaction temperature. The reaction is preferablycarried out in an inert gas atmosphere such as nitrogen, helium, argonor neon. In addition, although varying according to the types ofcompounds used and reaction temperature, the reaction may be carried outat decreased pressure, normal pressure or increased pressure, and thereaction pressure is generally within a range of from 20 to 1×10⁻⁶ Pa.There are no particular limitations on the reaction time (residence timein the case of a continuous process), and is generally from 0.001 to 50hours, preferably from 0.01 to 20 hours and more preferably from 0.1 to10 hours. In addition, the reaction can also be completed afterconfirming the formation of a desired amount of carbamic acid ester byliquid chromatography, for example, by sampling the reaction liquid, thereaction can be completed after confirming that the average degree ofpolymerization of aromatic polycarbonate present in the reaction liquidhas decreased to a prescribed value by, for example, gel permeationchromatography, or the reaction can be completed after confirming thatamino groups and/or carbonate groups have been consumed to a prescribedlevel by, for example, NMR.

In the present embodiment, a catalyst is preferably not used in thereaction between the aromatic polycarbonate and the amine compoundhaving primary amino groups. When a carbamic acid ester is heated in thepresence of a metal component derived from a catalyst during transportof the reaction mixture and a thermal decomposition reaction of carbamicacid ester contained in the reaction mixture to be described later, atendency may be observed in which a thermal denaturation reaction andthe like of the carbamic acid ester occurs easily. Although a catalystcan be used when carrying out the reaction between the aromaticpolycarbonate and the amine compound having primary amino groups, andtransfer of the reaction mixture and a thermal decomposition reactioncan be carried out after going through a step of removing the catalyst,this results in an increase in the number of steps, thereby making thisundesirable.

However, the use of a catalyst is not negated for the purpose ofcompleting the reaction in a short period of time, lowering the reactiontemperature and the like. In general, since aromatic amine compoundshave lower reactivity than aliphatic amines, in the case of using anaromatic amine compound for the amine compound, the use of a catalystmay be effective. In the case of using a catalyst, examples of catalyststhat can be used may include organic metal compounds and inorganic metalcompounds of tin, lead, copper or titanium, and basic catalysts such asalcoholates of alkaline metals or alkaline earth metals in the form ofmethylates, ethylates or butyrates (including isomers) of lithium,sodium, potassium, calcium or barium.

Although the reaction between the aromatic hydroxy compounds and theamine compounds having primary amino groups as described above can becarried out in the presence or absence of solvent, it is preferablycarried out in the presence of a solvent, and more preferably carriedout in a homogeneous solution in the presence of a solvent. Althoughthere are no particular limitations on the solvent, solvents thatdissolve or swell aromatic polycarbonates are preferable, and examplesof solvents that are used preferably may include aliphatic ethers suchas tetrahydrofuran or 1,4-dioxane; aromatic ethers such as diphenylether, di(methylphenyl)ether (including isomers), di(ethylphenyl)ether(including isomers) or di(propylphenyl)ether; aromatic hydrocarbons suchas benzene, toluene or xylene (including isomers); aromatic hydroxycompounds such as phenol; and halogen compounds such as methylenechloride, chloroform, carbon tetrachloride or chlorobenzene. Amongthese, aromatic hydroxy compounds are more preferable since they easilydissolve aromatic polycarbonates and the carbamic acid ester formed, anddemonstrate the effect of inhibiting the occurrence of thermaldenaturation reactions on the carbamic acid ester formed as will bedescribed later.

More preferably, the solvent is a monovalent aromatic hydroxy compoundhaving a single hydroxyl group directly bonded to the aromatichydrocarbon ring constituting the aromatic hydroxy compound. Although anaromatic hydroxy compound having two or more hydroxyl groups bondeddirectly to the aromatic hydrocarbon ring constituting the aromatichydroxy compound can also be used as an aromatic hydroxy compoundconstituting the composition of the present embodiment, since there arecases in which the viscosity of the solution increases in the reactionbetween the aromatic polycarbonate and the amine compound, this maycause a decrease in reaction efficiency or a decrease in efficiency whentransferring the reaction solution to be described later.

An aromatic hydroxy compound having at least one substituent R² asrepresented by the following formula (18) is preferable for themonovalent aromatic hydroxy compound mentioned above:

(wherein ring A represents an aromatic hydrocarbon ring which has 6 to20 carbon atoms, and which may have a substituent, and the ring A may bea monocyclic or heterocyclic ring,

R² represents an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups contain an atom selected from thegroup consisting of carbon, oxygen and nitrogen atoms, and R² may bondwith A to form a ring structure).

Examples of R² in formula (18) above may include aliphatic alkyl groupsin which the number of carbon atoms constituting the group is a numberselected from integers of from 1 to 20, such as a methyl group, an ethylgroup, a propyl group (including isomers), a butyl group (includingisomers), a pentyl group (including isomers), a hexyl group (includingisomers), a heptyl group (including isomers), an octyl group (includingisomers), a nonyl group (including isomers), a decyl group (includingisomers), a dodecyl group (including isomers) or an octadecyl group(including isomers); aliphatic alkoxy groups in which the number ofcarbon atoms constituting the group is a number selected from integersof from 1 to 20, such as a methoxy group, an ethoxy group, a propoxygroup (including isomers), a butyloxy group (including isomers), apentyloxy group (including isomers), a hexyloxy group (includingisomers), a heptyloxy group (including isomers), an octyloxy group(including isomers), a nonyloxy group (including isomers), a decyloxygroup (including isomers), a decyloxy group (including isomers), adodecyloxy group (including isomers) or an octadecyloxy group (includingisomers); aryl groups in which the number of carbon atoms constitutingthe group is from 6 to 20, such as a phenyl group, a methylphenyl group(including isomers), an ethylphenyl group (including isomers), apropylphenyl group (including isomers), a butylphenyl group (includingisomers), a pentylphenyl group (including isomers), a hexylphenyl group(including isomers), a heptylphenyl group (including isomers), anoctylphenyl group (including isomers), a nonylphenyl group (includingisomers), a decylphenyl group (including isomers), a biphenyl group(including isomers), a dimethylphenyl group (including isomers), adiethylphenyl group (including isomers), a dipropylphenyl group(including isomers), a dibutylphenyl group (including isomers), adipentylphenyl group (including isomers), a dihexylphenyl group(including isomers), a diheptylphenyl group (including isomers), aterphenyl group (including isomers), a trimethylphenyl group (includingisomers), a triethylphenyl group (including isomers), a tripropylphenylgroup (including isomers) or a tributylphenyl group (including isomers);aryloxy groups in which the number of carbon atoms constituting thegroup is from 6 to 20, such as a phenoxy group, a methylphenoxy group(including isomers), an ethylphenoxy group (including isomers), apropylphenoxy group (including isomers), a butylphenoxy group (includingisomers), a pentylphenoxy group (including isomers), a hexylphenoxygroup (including isomers), a heptylphenoxy group (including isomers), anoctylphenoxy group (including isomers), a nonylphenoxy group (includingisomers), a decylphenoxy group (including isomers), a phenylphenoxygroup (including isomers), a dimethylphenoxy group (including isomers),a diethylphenoxy group (including isomers), a dipropylphenoxy group(including isomers), a dibutylphenoxy group (including isomers), adipentylphenoxy group (including isomers), a dihexylphenoxy group(including isomers), a diheptylphenoxy group (including isomers), adiphenylphenoxy group (including isomers), a trimethylphenoxy group(including isomers), a triethylphenoxy group (including isomers), atripropylphenoxy group (including isomers) or a tributylphenoxy group(including isomers); aralkyl groups in which the number of carbon atomsconstituting the group is from 7 to 20, such as a phenylmethyl group, aphenylethyl group (including isomers), a phenylpropyl group (includingisomers), a phenylbutyl group (including isomers), a phenylpentyl group(including isomers), a phenylhexyl group (including isomers), aphenylheptyl group (including isomers), a phenyloctyl group (includingisomers) or a phenylnonyl group (including isomers); and aralkyloxygroups in which the number of carbon atoms constituting the group isfrom 7 to 20, such as a phenylmethoxy group, a phenylethoxy group(including isomers), a phenylpropyloxy group (including isomers), aphenylbutyloxy group (including isomers), a phenylpentyloxy group(including isomers), a phenylhexyloxy group (including isomers), aphenylheptyloxy group (including isomers), a phenyloctyloxy group(including isomers) or a phenylnonyloxy group (including isomers).

Examples of ring A in formula (18) above may include a benzene ring, anaphthalene ring, an anthracene ring, a phenanthracene ring, anaphthacene ring, a chrysene ring, a pyrene ring, a triphenylene ring, apentalene ring, an azulene ring, a heptalene ring, an indacene ring, abiphenylene ring, an acenaphthylene ring, an aceanthrylene ring and anacephenanthrylene ring, while preferable examples may include ringsselected from the group consisting of a benzene ring, a naphthalene ringand an anthracene ring. In addition, these rings may have a substituentother than the above-mentioned R², examples of which may includealiphatic alkyl groups in which the number of carbon atoms constitutingthe group is a number selected from integers of from 1 to 20, such as amethyl group, an ethyl group, a propyl group (including isomers), abutyl group (including isomers), a pentyl group (including isomers), ahexyl group (including isomers), a heptyl group (including isomers), anoctyl group (including isomers), a nonyl group (including isomers), adecyl group (including isomers), a dodecyl group (including isomers) oran octadecyl group (including isomers); aliphatic alkoxy groups in whichthe number of carbon atoms constituting the group is a number selectedfrom integers of from 1 to 20, such as a methoxy group, an ethoxy group,a propoxy group (including isomers), a butyloxy group (includingisomers), a pentyloxy group (including isomers), a hexyloxy group(including isomers), a heptyloxy group (including isomers), an octyloxygroup (including isomers), a nonyloxy group (including isomers), adecyloxy group (including isomers), a dodecyloxy group (includingisomers) or an octadecyloxy group (including isomers); aryl groups inwhich the number of carbon atoms constituting the group is from 6 to 20,such as a phenyl group, a methylphenyl group (including isomers), anethylphenyl group (including isomers), a propylphenyl group (includingisomers), a butylphenyl group (including isomers), a pentylphenyl group(including isomers), a hexylphenyl group (including isomers), aheptylphenyl group (including isomers), an octylphenyl group (includingisomers), a nonylphenyl group (including isomers), a decylphenyl group(including isomers), a biphenyl group (including isomers), adimethylphenyl group (including isomers), a diethylphenyl group(including isomers), a dipropylphenyl group (including isomers), adibutylphenyl group (including isomers), a dipentylphenyl group(including isomers), a dihexylphenyl group (including isomers), adiheptylphenyl group (including isomers), a terphenyl group (includingisomers), a trimethylphenyl group (including isomers), a triethylphenylgroup (including isomers), a tripropylphenyl group (including isomers)or a tributylphenyl group (including isomers); aryloxy groups in whichthe number of carbon atoms constituting the group is from 6 to 20, suchas a phenoxy group, a methylphenoxy group (including isomers), anethylphenoxy group (including isomers), a propylphenoxy group (includingisomers), a butylphenoxy group (including isomers), a pentylphenoxygroup (including isomers), a hexylphenoxy group (including isomers), aheptylphenoxy group (including isomers), an octylphenoxy group(including isomers), a nonylphenoxy group (including isomers), adecylphenoxy group (including isomers), a phenylphenoxy group (includingisomers), a dimethylphenoxy group (including isomers), a diethylphenoxygroup (including isomers), a dipropylphenoxy group (including isomers),a dibutylphenoxy group (including isomers), a dipentylphenoxy group(including isomers), a dihexylphenoxy group (including isomers), adiheptylphenoxy group (including isomers), a diphenylphenoxy group(including isomers), a trimethylphenoxy group (including isomers), atriethylphenoxy group (including isomers), a tripropylphenoxy group(including isomers) or a tributylphenoxy group (including isomers);aralkyl groups in which the number of carbon atoms constituting thegroup is from 7 to 20, such as a phenylmethyl group, a phenylethyl group(including isomers), a phenylpropyl group (including isomers), aphenylbutyl group (including isomers), a phenylpentyl group (includingisomers), a phenylhexyl group (including isomers), a phenylheptyl group(including isomers), a phenyloctyl group (including isomers) or aphenylnonyl group (including isomers); and aralkyloxy groups in whichthe number of carbon atoms constituting the group is from 7 to 20, suchas a phenylmethoxy group, a phenylethoxy group (including isomers), aphenylpropyloxy group (including isomers), a phenylbutyloxy group(including isomers), a phenylpentyloxy group (including isomers), aphenylhexyloxy group (including isomers), a phenylheptyloxy group(including isomers), a phenyloctyloxy group (including isomers) or aphenylnonyloxy group (including isomers).

Examples of such monovalent aromatic hydroxy compounds may includemono-substituted phenols such as phenol, methyl-phenol (includingisomers), ethyl-phenol (including isomers), propyl-phenol (includingisomers), butyl-phenol (including isomers), pentyl-phenol (includingisomers), hexyl-phenol (including isomers), heptyl-phenol (includingisomers), octyl-phenol (including isomers), nonyl-phenol (includingisomers), decyl-phenol (including isomers), dodecyl-phenol (includingisomers), phenyl-phenol (including isomers), phenoxyphenol (includingisomers) or cumyl-phenol (including isomers); di-substituted phenolssuch as dimethyl-phenol (including isomers), diethyl-phenol (includingisomers), dipropyl-phenol (including isomers), dibutyl-phenol (includingisomers), dipentyl-phenol (including isomers), dihexyl-phenol (includingisomers), diheptyl-phenol (including isomers), dioctyl-phenol (includingisomers), dinonyl-phenol (including isomers), didecyl-phenol (includingisomers), didodecyl-phenol (including isomers), diphenyl-phenol(including isomers), diphenoxyphenol (including isomers), dicumyl-phenol(including isomers), methyl-ethyl-phenol (including isomers),methyl-propyl-phenol (including isomers), methyl-butyl-phenol (includingisomers), methyl-pentyl-phenol (including isomers), methyl-hexyl-phenol(including isomers), methyl-heptyl-phenol (including isomers),methyl-octyl-phenol (including isomers), methyl-nonyl-phenol (includingisomers), methyl-decyl-phenol (including isomers), methyl-dodecyl-phenol(including isomers), methyl-phenyl-phenol (including isomers),methyl-phenoxyphenol (including isomers), methyl-cumyl-phenol (includingisomers), ethyl-propyl-phenol (including isomers), ethyl-butyl-phenol(including isomers), ethyl-pentyl-phenol (including isomers),ethyl-hexyl-phenol (including isomers), ethyl-heptyl-phenol (includingisomers), ethyl-octyl-phenol (including isomers), ethyl-nonyl-phenol(including isomers), ethyl-decyl-phenol (including isomers),ethyl-dodecyl-phenol (including isomers), ethyl-phenyl-phenol (includingisomers), ethyl-phenoxyphenol (including isomers), ethyl-cumyl-phenol(including isomers), propyl-butyl-phenol (including isomers),propyl-pentyl-phenol (including isomers), propyl-hexyl-phenol (includingisomers), propyl-heptyl-phenol (including isomers), propyl-octyl-phenol(including isomers), propyl-nonyl-phenol (including isomers),propyl-decyl-phenol (including isomers), propyl-dodecyl-phenol(including isomers), propyl-phenyl-phenol (including isomers),propyl-phenoxyphenol (including isomers), propyl-cumyl-phenol (includingisomers), butyl-pentyl-phenol (including isomers), butyl-hexyl-phenol(including isomers), butyl-heptyl-phenol (including isomers),butyl-octyl-phenol (including isomers), butyl-nonyl-phenol (includingisomers), butyl-decyl-phenol (including isomers), butyl-dodecyl-phenol(including isomers), butyl-phenyl-phenol (including isomers),butyl-phenoxyphenol (including isomers), butyl-cumyl-phenol (includingisomers), pentyl-hexyl-phenol (including isomers), pentyl-heptyl-phenol(including isomers), pentyl-octyl-phenol (including isomers),pentyl-nonyl-phenol (including isomers), pentyl-decyl-phenol (includingisomers), pentyl-dodecyl-phenol (including isomers),pentyl-phenyl-phenol (including isomers), pentyl-phenoxyphenol(including isomers), pentyl-cumyl-phenol (including isomers),hexyl-heptyl-phenol (including isomers), hexyl-octyl-phenol (includingisomers), hexyl-nonyl-phenol (including isomers), hexyl-decyl-phenol(including isomers), hexyl-dodecyl-phenol (including isomers),hexyl-phenyl-phenol (including isomers), hexyl-phenoxyphenol (includingisomers), hexyl-cumyl-phenol (including isomers), heptyl-octyl-phenol(including isomers), heptyl-nonyl-phenol (including isomers),heptyl-decyl-phenol (including isomers), heptyl-dodecyl-phenol(including isomers), heptyl-phenyl-phenol (including isomers),heptyl-phenoxyphenol (including isomers), heptyl-cumyl-phenol (includingisomers), octyl-nonyl-phenol (including isomers), octyl-decyl-phenol(including isomers), octyl-dodecyl-phenol (including isomers),octyl-phenyl-phenol (including isomers), octyl-phenoxyphenol (includingisomers), octyl-cumyl-phenol (including isomers), nonyl-decyl-phenol(including isomers), nonyl-dodecyl-phenol (including isomers),nonyl-phenyl-phenol (including isomers), nonyl-phenoxyphenol (includingisomers), nonyl-cumyl-phenol (including isomers), dodecyl-phenyl-phenol(including isomers), dodecyl-phenoxyphenol (including isomers) ordodecyl-cumyl-phenol (including isomers); and tri-substituted phenolssuch as trimethyl-phenol (including isomers), triethyl-phenol (includingisomers), tripropyl-phenol (including isomers), tributyl-phenol(including isomers), tripentyl-phenol (including isomers),trihexyl-phenol (including isomers), triheptyl-phenol (includingisomers), trioctyl-phenol (including isomers), trinonyl-phenol(including isomers), tridecyl-phenol (including isomers),tridodecyl-phenol (including isomers), triphenyl-phenol (includingisomers), triphenoxyphenol (including isomers), tricumyl-phenol(including isomers), dimethyl-ethyl-phenol (including isomers),dimethyl-propyl-phenol (including isomers), dimethyl-butyl-phenol(including isomers), dimethyl-pentyl-phenol (including isomers),dimethyl-hexyl-phenol (including isomers), dimethyl-heptyl-phenol(including isomers), dimethyl-octyl-phenol (including isomers),dimethyl-nonyl-phenol (including isomers), dimethyl-decyl-phenol(including isomers), dimethyl-dodecyl-phenol (including isomers),dimethyl-phenyl-phenol (including isomers), dimethyl-phenoxyphenol(including isomers), dimethyl-cumyl-phenol (including isomers),diethyl-methyl-phenol (including isomers), diethyl-propyl-phenol(including isomers), diethyl-butyl-phenol (including isomers),diethyl-pentyl-phenol (including isomers), diethyl-hexyl-phenol(including isomers), diethyl-heptyl-phenol (including isomers),diethyl-octyl-phenol (including isomers), diethyl-nonyl-phenol(including isomers), diethyl-decyl-phenol (including isomers),diethyl-dodecyl-phenol (including isomers), diethyl-phenyl-phenol(including isomers), diethyl-phenoxyphenol (including isomers),diethyl-cumyl-phenol (including isomers), dipropyl-methyl-phenol(including isomers), dipropyl-ethyl-phenol (including isomers),dipropyl-butyl-phenol (including isomers), dipropyl-pentyl-phenol(including isomers), dipropyl-hexyl-phenol (including isomers),dipropyl-heptyl-phenol (including isomers), dipropyl-octyl-phenol(including isomers), dipropyl-nonyl-phenol (including isomers),dipropyl-decyl-phenol (including isomers), dipropyl-dodecyl-phenol(including isomers), dipropyl-phenyl-phenol (including isomers),dipropyl-phenoxyphenol (including isomers), dipropyl-cumyl-phenol(including isomers), dibutyl-methyl-phenol (including isomers),dibutyl-ethyl-phenol (including isomers), dibutyl-propyl-phenol(including isomers), dibutyl-pentyl-phenol (including isomers),dibutyl-hexyl-phenol (including isomers), dibutyl-heptyl-phenol(including isomers), dibutyl-octyl-phenol (including isomers),dibutyl-nonyl-phenol (including isomers), dibutyl-decyl-phenol(including isomers), dibutyl-dodecyl-phenol (including isomers),dibutyl-phenyl-phenol (including isomers), dibutyl-phenoxyphenol(including isomers), dibutyl-cumyl-phenol (including isomers),dipentyl-methyl-phenol (including isomers), dipentyl-ethyl-phenol(including isomers), dipentyl-propyl-phenol (including isomers),dipentyl-butyl-phenol (including isomers), dipentyl-hexyl-phenol(including isomers), dipentyl-heptyl-phenol (including isomers),dipentyl-octyl-phenol (including isomers), dipentyl-nonyl-phenol(including isomers), dipentyl-decyl-phenol (including isomers),dipentyl-dodecyl-phenol (including isomers), dipentyl-phenyl-phenol(including isomers), dipentyl-phenoxyphenol (including isomers),dipentyl-cumyl-phenol (including isomers), dihexyl-methyl-phenol(including isomers), dihexyl-ethyl-phenol (including isomers),dihexyl-propyl-phenol (including isomers), dihexyl-butyl-phenol(including isomers), dihexyl-pentyl-phenol (including isomers),dihexyl-heptyl-phenol (including isomers), dihexyl-octyl-phenol(including isomers), dihexyl-nonyl-phenol (including isomers),dihexyl-decyl-phenol (including isomers), dihexyl-dodecyl-phenol(including isomers), dihexyl-phenyl-phenol (including isomers),dihexyl-phenoxyphenol (including isomers), dihexyl-cumyl-phenol(including isomers), diheptyl-methyl-phenol (including isomers),diheptyl-ethyl-phenol (including isomers), diheptyl-propyl-phenol(including isomers), diheptyl-butyl-phenol (including isomers),diheptyl-pentyl-phenol (including isomers), diheptyl-hexyl-phenol(including isomers), diheptyl-octyl-phenol (including isomers),diheptyl-nonyl-phenol (including isomers), diheptyl-decyl-phenol(including isomers), diheptyl-dodecyl-phenol (including isomers),diheptyl-phenyl-phenol (including isomers), diheptyl-phenoxyphenol(including isomers), diheptyl-cumyl-phenol (including isomers),dioctyl-methyl-phenol (including isomers), dioctyl-ethyl-phenol(including isomers), dioctyl-propyl-phenol (including isomers),dioctyl-butyl-phenol (including isomers), dioctyl-pentyl-phenol(including isomers), dioctyl-hexyl-phenol (including isomers),dioctyl-heptyl-phenol (including isomers), dioctyl-nonyl-phenol(including isomers), dioctyl-decyl-phenol (including isomers),dioctyl-dodecyl-phenol (including isomers), dioctyl-phenyl-phenol(including isomers), dioctyl-phenoxyphenol (including isomers),dioctyl-cumyl-phenol (including isomers), dinonyl-methyl-phenol(including isomers), dinonyl-ethyl-phenol (including isomers),dinonyl-propyl-phenol (including isomers), dinonyl-butyl-phenol(including isomers), dinonyl-pentyl-phenol (including isomers),dinonyl-hexyl-phenol (including isomers), dinonyl-heptyl-phenol(including isomers), dinonyl-octyl-phenol (including isomers),dinonyl-decyl-phenol (including isomers), dinonyl-dodecyl-phenol(including isomers), dinonyl-phenyl-phenol (including isomers),dinonyl-phenoxyphenol (including isomers), dinonyl-cumyl-phenol(including isomers), didecyl-methyl-phenol (including isomers),didecyl-ethyl-phenol (including isomers), didecyl-propyl-phenol(including isomers), didecyl-butyl-phenol (including isomers),didecyl-pentyl-phenol (including isomers), didecyl-hexyl-phenol(including isomers), didecyl-heptyl-phenol (including isomers),didecyl-octyl-phenol (including isomers), didecyl-nonyl-phenol(including isomers), didecyl-dodecyl-phenol (including isomers),didecyl-phenyl-phenol (including isomers), didecyl-phenoxyphenol(including isomers), didecyl-cumyl-phenol (including isomers),didodecyl-methyl-phenol (including isomers), didodecyl-ethyl-phenol(including isomers), didodecyl-propyl-phenol (including isomers),didodecyl-butyl-phenol (including isomers), didodecyl-pentyl-phenol(including isomers), didodecyl-hexyl-phenol (including isomers),didodecyl-heptyl-phenol (including isomers), didodecyl-octyl-phenol(including isomers), didodecyl-nonyl-phenol (including isomers),didodecyl-decyl-phenol (including isomers), didodecyl-dodecyl-phenol(including isomers), didodecyl-phenyl-phenol (including isomers),didodecyl-phenoxyphenol (including isomers), didodecyl-cumyl-phenol(including isomers), diphenyl-methyl-phenol (including isomers),diphenyl-ethyl-phenol (including isomers), diphenyl-propyl-phenol(including isomers), diphenyl-butyl-phenol (including isomers),diphenyl-pentyl-phenol (including isomers), diphenyl-hexyl-phenol(including isomers), diphenyl-heptyl-phenol (including isomers),diphenyl-octyl-phenol (including isomers), diphenyl-nonyl-phenol(including isomers), diphenyl-decyl-phenol (including isomers),diphenyl-dodecyl-phenol (including isomers), diphenyl-phenoxyphenol(including isomers), diphenyl-cumyl-phenol (including isomers),diphenoxymethyl-phenol (including isomers), diphenoxyethyl-phenol(including isomers), diphenoxypropyl-phenol (including isomers),diphenoxybutyl-phenol (including isomers), diphenoxypentyl-phenol(including isomers), diphenoxyhexyl-phenol (including isomers),diphenoxyheptyl-phenol (including isomers), diphenoxyoctyl-phenol(including isomers), diphenoxynonyl-phenol (including isomers),diphenoxydecyl-phenol (including isomers), diphenoxydodecyl-phenol(including isomers), diphenoxyphenyl-phenol (including isomers),diphenoxycumyl-phenol (including isomers), dicumyl-methyl-phenol(including isomers), dicumyl-ethyl-phenol (including isomers),dicumyl-propyl-phenol (including isomers), dicumyl-butyl-phenol(including isomers), dicumyl-pentyl-phenol (including isomers),dicumyl-hexyl-phenol (including isomers), dicumyl-heptyl-phenol(including isomers), dicumyl-octyl-phenol (including isomers),dicumyl-nonyl-phenol (including isomers), dicumyl-decyl-phenol(including isomers), dicumyl-dodecyl-phenol (including isomers),dicumyl-phenyl-phenol (including isomers), dicumyl-phenoxyphenol(including isomers), methyl-ethyl-propyl-phenol (including isomers),methyl-ethyl-butyl-phenol (including isomers),methyl-ethyl-pentyl-phenol (including isomers),methyl-ethyl-hexyl-phenol (including isomers),methyl-ethyl-heptyl-phenol (including isomers),methyl-ethyl-octyl-phenol (including isomers), methyl-ethyl-nonyl-phenol(including isomers), methyl-ethyl-decyl-phenol (including isomers),methyl-ethyl-dodecyl-phenol (including isomers),methyl-ethyl-phenyl-phenol (including isomers),methyl-ethyl-phenoxyphenol (including isomers),methyl-ethyl-cumyl-phenol (including isomers),methyl-propyl-butyl-phenol (including isomers),methyl-propyl-pentyl-phenol (including isomers),methyl-propyl-hexyl-phenol (including isomers),methyl-propyl-heptyl-phenol (including isomers),methyl-propyl-octyl-phenol (including isomers),methyl-propyl-nonyl-phenol (including isomers),methyl-propyl-decyl-phenol (including isomers),methyl-propyl-dodecyl-phenol (including isomers),methyl-propyl-phenyl-phenol (including isomers),methyl-propyl-phenoxyphenol (including isomers),methyl-propyl-cumyl-phenol (including isomers),methyl-butyl-pentyl-phenol (including isomers),methyl-butyl-hexyl-phenol (including isomers),methyl-butyl-heptyl-phenol (including isomers),methyl-butyl-octyl-phenol (including isomers), methyl-butyl-nonyl-phenol(including isomers), methyl-butyl-decyl-phenol (including isomers),methyl-butyl-dodecyl-phenol (including isomers),methyl-butyl-phenyl-phenol (including isomers),methyl-butyl-phenoxyphenol (including isomers),methyl-butyl-cumyl-phenol (including isomers),methyl-pentyl-hexyl-phenol (including isomers),methyl-pentyl-heptyl-phenol (including isomers),methyl-pentyl-octyl-phenol (including isomers),methyl-pentyl-nonyl-phenol (including isomers),methyl-pentyl-decyl-phenol (including isomers),methyl-pentyl-dodecyl-phenol (including isomers),methyl-pentyl-phenyl-phenol (including isomers),methyl-pentyl-phenoxyphenol (including isomers),methyl-pentyl-cumyl-phenol (including isomers),methyl-hexyl-heptyl-phenol (including isomers),methyl-hexyl-octyl-phenol (including isomers), methyl-hexyl-nonyl-phenol(including isomers), methyl-hexyl-decyl-phenol (including isomers),methyl-hexyl-dodecyl-phenol (including isomers),methyl-hexyl-phenyl-phenol (including isomers),methyl-hexyl-phenoxyphenol (including isomers),methyl-hexyl-cumyl-phenol (including isomers), ethyl-propyl-butyl-phenol(including isomers), ethyl-propyl-pentyl-phenol (including isomers),ethyl-propyl-hexyl-phenol (including isomers),ethyl-propyl-heptyl-phenol (including isomers),ethyl-propyl-octyl-phenol (including isomers), ethyl-propyl-nonyl-phenol(including isomers), ethyl-propyl-decyl-phenol (including isomers),ethyl-propyl-dodecyl-phenol (including isomers),ethyl-propyl-phenyl-phenol (including isomers),ethyl-propyl-phenoxyphenol (including isomers),ethyl-propyl-cumyl-phenol (including isomers), ethyl-butyl-phenol(including isomers), ethyl-butyl-pentyl-phenol (including isomers),ethyl-butyl-hexyl-phenol (including isomers), ethyl-butyl-heptyl-phenol(including isomers), ethyl-butyl-octyl-phenol (including isomers),ethyl-butyl-nonyl-phenol (including isomers), ethyl-butyl-decyl-phenol(including isomers), ethyl-butyl-dodecyl-phenol (including isomers),ethyl-butyl-phenyl-phenol (including isomers), ethyl-butyl-phenoxyphenol(including isomers), ethyl-butyl-cumyl-phenol (including isomers),ethyl-pentyl-hexyl-phenol (including isomers),ethyl-pentyl-heptyl-phenol (including isomers),ethyl-pentyl-octyl-phenol (including isomers), ethyl-pentyl-nonyl-phenol(including isomers), ethyl-pentyl-decyl-phenol (including isomers),ethyl-pentyl-dodecyl-phenol (including isomers),ethyl-pentyl-phenyl-phenol (including isomers),ethyl-pentyl-phenoxyphenol (including isomers),ethyl-pentyl-cumyl-phenol (including isomers), ethyl-hexyl-heptyl-phenol(including isomers), ethyl-hexyl-octyl-phenol (including isomers),ethyl-hexyl-nonyl-phenol (including isomers), ethyl-hexyl-decyl-phenol(including isomers), ethyl-hexyl-dodecyl-phenol (including isomers),ethyl-hexyl-phenyl-phenol (including isomers), ethyl-hexyl-phenoxyphenol(including isomers), ethyl-hexyl-cumyl-phenol (including isomers),ethyl-heptyl-octyl-phenol (including isomers), ethyl-heptyl-nonyl-phenol(including isomers), ethyl-heptyl-decyl-phenol (including isomers),ethyl-heptyl-dodecyl-phenol (including isomers),ethyl-heptyl-phenyl-phenol (including isomers),ethyl-heptyl-phenoxyphenol (including isomers),ethyl-heptyl-cumyl-phenol (including isomers), ethyl-octyl-phenol(including isomers), ethyl-octyl-nonyl-phenol (including isomers),ethyl-octyl-decyl-phenol (including isomers), ethyl-octyl-dodecyl-phenol(including isomers), ethyl-octyl-phenyl-phenol (including isomers),ethyl-octyl-phenoxyphenol (including isomers), ethyl-octyl-cumyl-phenol(including isomers), ethyl-nonyl-decyl-phenol (including isomers),ethyl-nonyl-dodecyl-phenol (including isomers),ethyl-nonyl-phenyl-phenol (including isomers), ethyl-nonyl-phenoxyphenol(including isomers), ethyl-nonyl-cumyl-phenol (including isomers),ethyl-decyl-dodecyl-phenol (including isomers),ethyl-decyl-phenyl-phenol (including isomers), ethyl-decyl-phenoxyphenol(including isomers), ethyl-decyl-cumyl-phenol (including isomers),ethyl-dodecyl-phenyl-phenol (including isomers),ethyl-dodecyl-phenoxyphenol (including isomers),ethyl-dodecyl-cumyl-phenol (including isomers),ethyl-phenyl-phenoxyphenol (including isomers),ethyl-phenyl-cumyl-phenol (including isomers), propyl-butyl-phenol(including isomers), propyl-butyl-pentyl-phenol (including isomers),propyl-butyl-hexyl-phenol (including isomers),propyl-butyl-heptyl-phenol (including isomers),propyl-butyl-octyl-phenol (including isomers), propyl-butyl-nonyl-phenol(including isomers), propyl-butyl-decyl-phenol (including isomers),propyl-butyl-dodecyl-phenol (including isomers),propyl-butyl-phenyl-phenol (including isomers),propyl-butyl-phenoxyphenol (including isomers),propyl-butyl-cumyl-phenol (including isomers), propyl-pentyl-phenol(including isomers), propyl-pentyl-hexyl-phenol (including isomers),propyl-pentyl-heptyl-phenol (including isomers),propyl-pentyl-octyl-phenol (including isomers),propyl-pentyl-nonyl-phenol (including isomers),propyl-pentyl-decyl-phenol (including isomers),propyl-pentyl-dodecyl-phenol (including isomers),propyl-pentyl-phenyl-phenol (including isomers),propyl-pentyl-phenoxyphenol (including isomers),propyl-pentyl-cumyl-phenol (including isomers), propyl-hexyl-phenol(including isomers), propyl-hexyl-heptyl-phenol (including isomers),propyl-hexyl-octyl-phenol (including isomers), propyl-hexyl-nonyl-phenol(including isomers), propyl-hexyl-decyl-phenol (including isomers),propyl-hexyl-dodecyl-phenol (including isomers),propyl-hexyl-phenyl-phenol (including isomers),propyl-hexyl-phenoxyphenol (including isomers),propyl-hexyl-cumyl-phenol (including isomers),propyl-heptyl-octyl-phenol (including isomers),propyl-heptyl-nonyl-phenol (including isomers),propyl-heptyl-decyl-phenol (including isomers),propyl-heptyl-dodecyl-phenol (including isomers),propyl-heptyl-phenyl-phenol (including isomers),propyl-heptyl-phenoxyphenol (including isomers),propyl-heptyl-cumyl-phenol (including isomers),propyl-octyl-nonyl-phenol (including isomers), propyl-octyl-decyl-phenol(including isomers), propyl-octyl-dodecyl-phenol (including isomers),propyl-octyl-phenyl-phenol (including isomers),propyl-octyl-phenoxyphenol (including isomers),propyl-octyl-cumyl-phenol (including isomers), propyl-nonyl-decyl-phenol(including isomers), propyl-nonyl-dodecyl-phenol (including isomers),propyl-nonyl-phenyl-phenol (including isomers),propyl-nonyl-phenoxyphenol (including isomers),propyl-nonyl-cumyl-phenol (including isomers),propyl-decyl-dodecyl-phenol (including isomers),propyl-decyl-phenyl-phenol (including isomers),propyl-decyl-phenoxyphenol (including isomers),propyl-decyl-cumyl-phenol (including isomers),propyl-dodecyl-phenyl-phenol (including isomers),propyl-dodecyl-phenoxyphenol (including isomers),propyl-dodecyl-cumyl-phenol (including isomers), methyl-phenol(including isomers), ethyl-phenol (including isomers), propyl-phenol(including isomers), butyl-phenol (including isomers), pentyl-phenol(including isomers), hexyl-phenol (including isomers), heptyl-phenol(including isomers), octyl-phenol (including isomers), nonyl-phenol(including isomers), decyl-phenol (including isomers), dodecyl-phenol(including isomers), phenyl-phenol (including isomers), phenoxyphenol(including isomers) cumyl-phenol (including isomers)propyl-phenyl-phenoxyphenol (including isomers),propyl-phenyl-cumyl-phenol (including isomers),propyl-phenoxycumyl-phenol (including isomers),propyl-butyl-pentyl-phenol (including isomers),propyl-butyl-hexyl-phenol (including isomers),propyl-butyl-heptyl-phenol (including isomers),propyl-butyl-octyl-phenol (including isomers), propyl-butyl-nonyl-phenol(including isomers), propyl-butyl-decyl-phenol (including isomers),propyl-butyl-dodecyl-phenol (including isomers),propyl-butyl-phenyl-phenol (including isomers),propyl-butyl-phenoxyphenol (including isomers),propyl-butyl-cumyl-phenol (including isomers), propyl-pentyl-phenol(including isomers), propyl-pentyl-hexyl-phenol (including isomers),propyl-pentyl-heptyl-phenol (including isomers),propyl-pentyl-octyl-phenol (including isomers),propyl-pentyl-nonyl-phenol (including isomers),propyl-pentyl-decyl-phenol (including isomers),propyl-pentyl-dodecyl-phenol (including isomers),propyl-pentyl-phenyl-phenol (including isomers),propyl-pentyl-phenoxyphenol (including isomers),propyl-pentyl-cumyl-phenol (including isomers),propyl-hexyl-heptyl-phenol (including isomers),propyl-hexyl-octyl-phenol (including isomers), propyl-hexyl-nonyl-phenol(including isomers), propyl-hexyl-decyl-phenol (including isomers),propyl-hexyl-dodecyl-phenol (including isomers),propyl-hexyl-phenyl-phenol (including isomers),propyl-hexyl-phenoxyphenol (including isomers),propyl-hexyl-cumyl-phenol (including isomers),propyl-heptyl-octyl-phenol (including isomers),propyl-heptyl-nonyl-phenol (including isomers),propyl-heptyl-decyl-phenol (including isomers),propyl-heptyl-dodecyl-phenol (including isomers),propyl-heptyl-phenyl-phenol (including isomers),propyl-heptyl-phenoxyphenol (including isomers),propyl-heptyl-cumyl-phenol (including isomers),propyl-octyl-nonyl-phenol (including isomers), propyl-octyl-decyl-phenol(including isomers), propyl-octyl-dodecyl-phenol (including isomers),propyl-octyl-phenyl-phenol (including isomers),propyl-octyl-phenoxyphenol (including isomers),propyl-octyl-cumyl-phenol (including isomers), propyl-nonyl-decyl-phenol(including isomers), propyl-nonyl-dodecyl-phenol (including isomers),propyl-nonyl-phenyl-phenol (including isomers),propyl-nonyl-phenoxyphenol (including isomers),propyl-nonyl-cumyl-phenol (including isomers),propyl-decyl-dodecyl-phenol (including isomers),propyl-decyl-phenyl-phenol (including isomers),propyl-decyl-phenoxyphenol (including isomers),propyl-decyl-cumyl-phenol (including isomers),propyl-dodecyl-phenyl-phenol (including isomers),propyl-dodecyl-phenoxyphenol (including isomers), cumyl-phenol(including isomers) propyl-phenyl-phenoxyphenol (including isomers),propyl-phenyl-cumyl-phenol (including isomers),butyl-pentyl-hexyl-phenol (including isomers),butyl-pentyl-heptyl-phenol (including isomers),butyl-pentyl-octyl-phenol (including isomers), butyl-pentyl-nonyl-phenol(including isomers), butyl-pentyl-decyl-phenol (including isomers),butyl-pentyl-dodecyl-phenol (including isomers),butyl-pentyl-phenyl-phenol (including isomers),butyl-pentyl-phenoxyphenol (including isomers),butyl-pentyl-cumyl-phenol (including isomers), butyl-hexyl-heptyl-phenol(including isomers), butyl-hexyl-octyl-phenol (including isomers),butyl-hexyl-nonyl-phenol (including isomers), butyl-hexyl-decyl-phenol(including isomers), butyl-hexyl-dodecyl-phenol (including isomers),butyl-hexyl-phenyl-phenol (including isomers), butyl-hexyl-phenoxyphenol(including isomers), butyl-hexyl-cumyl-phenol (including isomers),butyl-heptyl-octyl-phenol (including isomers), butyl-heptyl-nonyl-phenol(including isomers), butyl-heptyl-decyl-phenol (including isomers),butyl-heptyl-dodecyl-phenol (including isomers),butyl-heptyl-phenyl-phenol (including isomers),butyl-heptyl-phenoxyphenol (including isomers),butyl-heptyl-cumyl-phenol (including isomers), butyl-octyl-nonyl-phenol(including isomers), butyl-octyl-decyl-phenol (including isomers),butyl-octyl-dodecyl-phenol (including isomers),butyl-octyl-phenyl-phenol (including isomers), butyl-octyl-phenoxyphenol(including isomers), butyl-octyl-cumyl-phenol (including isomers),butyl-nonyl-decyl-phenol (including isomers), butyl-nonyl-dodecyl-phenol(including isomers), butyl-nonyl-phenyl-phenol (including isomers),butyl-nonyl-phenoxyphenol (including isomers), butyl-nonyl-cumyl-phenol(including isomers), butyl-decyl-dodecyl-phenol (including isomers),butyl-decyl-phenyl-phenol (including isomers), butyl-decyl-phenoxyphenol(including isomers), butyl-decyl-cumyl-phenol (including isomers),butyl-dodecyl-phenol (including isomers), butyl-dodecyl-phenyl-phenol(including isomers), butyl-dodecyl-phenoxyphenol (including isomers),butyl-dodecyl-cumyl-phenol (including isomers), butyl-phenyl-phenol(including isomers), butyl-phenyl-phenoxyphenol (including isomers),butyl-phenyl-cumyl-phenol (including isomers),pentyl-hexyl-heptyl-phenol (including isomers),pentyl-hexyl-octyl-phenol (including isomers), pentyl-hexyl-nonyl-phenol(including isomers), pentyl-hexyl-decyl-phenol (including isomers),pentyl-hexyl-dodecyl-phenol (including isomers),pentyl-hexyl-phenyl-phenol (including isomers),pentyl-hexyl-phenoxyphenol (including isomers),pentyl-hexyl-cumyl-phenol (including isomers),pentyl-heptyl-octyl-phenol (including isomers),pentyl-heptyl-nonyl-phenol (including isomers),pentyl-heptyl-decyl-phenol (including isomers),pentyl-heptyl-dodecyl-phenol (including isomers),pentyl-heptyl-phenyl-phenol (including isomers),pentyl-heptyl-phenoxyphenol (including isomers),pentyl-heptyl-cumyl-phenol (including isomers),pentyl-octyl-nonyl-phenol (including isomers), pentyl-octyl-decyl-phenol(including isomers), pentyl-octyl-dodecyl-phenol (including isomers),pentyl-octyl-phenyl-phenol (including isomers),pentyl-octyl-phenoxyphenol (including isomers),pentyl-octyl-cumyl-phenol (including isomers), pentyl-nonyl-decyl-phenol(including isomers), pentyl-nonyl-dodecyl-phenol (including isomers),pentyl-nonyl-phenyl-phenol (including isomers),pentyl-nonyl-phenoxyphenol (including isomers),pentyl-nonyl-cumyl-phenol (including isomers),pentyl-decyl-dodecyl-phenol (including isomers),pentyl-decyl-phenyl-phenol (including isomers),pentyl-decyl-phenoxyphenol (including isomers),pentyl-decyl-cumyl-phenol (including isomers),pentyl-decyl-dodecyl-phenol (including isomers),pentyl-decyl-phenyl-phenol (including isomers),pentyl-decyl-phenoxyphenol (including isomers),pentyl-decyl-cumyl-phenol (including isomers),pentyl-dodecyl-phenyl-phenol (including isomers),pentyl-dodecyl-phenoxyphenol (including isomers),pentyl-dodecyl-cumyl-phenol (including isomers),pentyl-phenyl-phenoxyphenol (including isomers),pentyl-phenyl-cumyl-phenol (including isomers),hexyl-heptyl-octyl-phenol (including isomers), hexyl-heptyl-nonyl-phenol(including isomers), hexyl-heptyl-decyl-phenol (including isomers),hexyl-heptyl-dodecyl-phenol (including isomers),hexyl-heptyl-phenyl-phenol (including isomers),hexyl-heptyl-phenoxyphenol (including isomers),hexyl-heptyl-cumyl-phenol (including isomers), hexyl-octyl-nonyl-phenol(including isomers), hexyl-octyl-decyl-phenol (including isomers),hexyl-octyl-dodecyl-phenol (including isomers),hexyl-octyl-phenyl-phenol (including isomers), hexyl-octyl-phenoxyphenol(including isomers), hexyl-octyl-cumyl-phenol (including isomers),hexyl-nonyl-decyl-phenol (including isomers), hexyl-nonyl-dodecyl-phenol(including isomers), hexyl-nonyl-phenyl-phenol (including isomers),hexyl-nonyl-phenoxyphenol-decyl-dodecyl-phenol (including isomers),hexyl-decyl-phenyl-phenol (including isomers), hexyl-decyl-phenoxyphenol(including isomers), hexyl-decyl-cumyl-phenol (including isomers),hexyl-dodecyl-phenyl-phenol (including isomers),hexyl-dodecyl-phenoxyphenol (including isomers),hexyl-dodecyl-cumyl-phenol (including isomers),hexyl-phenyl-phenoxyphenol (including isomers),hexyl-phenyl-cumyl-phenol (including isomers), heptyl-octyl-nonyl-phenol(including isomers), heptyl-octyl-decyl-phenol (including isomers),heptyl-octyl-dodecyl-phenol (including isomers),heptyl-octyl-phenyl-phenol (including isomers),heptyl-octyl-phenoxyphenol (including isomers),heptyl-octyl-cumyl-phenol (including isomers), heptyl-nonyl-decyl-phenol(including isomers), heptyl-nonyl-dodecyl-phenol (including isomers),heptyl-nonyl-phenyl-phenol (including isomers),heptyl-nonyl-phenoxyphenol (including isomers),heptyl-nonyl-cumyl-phenol (including isomers),heptyl-decyl-dodecyl-phenol (including isomers),heptyl-decyl-phenyl-phenol (including isomers),heptyl-decyl-phenoxyphenol (including isomers),heptyl-decyl-cumyl-phenol (including isomers),heptyl-dodecyl-phenyl-phenol (including isomers),heptyl-dodecyl-phenoxyphenol (including isomers),heptyl-dodecyl-cumyl-phenol (including isomers),heptyl-phenyl-phenoxyphenol (including isomers),heptyl-phenyl-cumyl-phenol (including isomers), octyl-nonyl-decyl-phenol(including isomers), octyl-nonyl-dodecyl-phenol (including isomers),octyl-nonyl-phenyl-phenol (including isomers), octyl-nonyl-phenoxyphenol(including isomers), octyl-nonyl-cumyl-phenol (including isomers),octyl-decyl-dodecyl-phenol (including isomers),octyl-decyl-phenyl-phenol (including isomers), octyl-decyl-phenoxyphenol(including isomers), octyl-decyl-cumyl-phenol (including isomers),octyl-dodecyl-phenyl-phenol (including isomers),octyl-dodecyl-phenoxyphenol (including isomers),octyl-dodecyl-cumyl-phenol (including isomers),octyl-dodecyl-phenyl-phenol (including isomers),octyl-dodecyl-phenoxyphenol (including isomers),octyl-dodecyl-cumyl-phenol (including isomers),octyl-phenyl-phenoxyphenol (including isomers),octyl-phenyl-cumyl-phenol (including isomers),nonyl-decyl-dodecyl-phenol (including isomers),nonyl-decyl-phenyl-phenol (including isomers), nonyl-decyl-phenoxyphenol(including isomers), nonyl-decyl-cumyl-phenol (including isomers),nonyl-dodecyl-phenyl-phenol (including isomers),nonyl-dodecyl-phenoxyphenol (including isomers),nonyl-dodecyl-cumyl-phenol (including isomers),nonyl-phenyl-phenoxyphenol (including isomers),nonyl-phenyl-cumyl-phenol (including isomers),decyl-dodecyl-phenyl-phenol (including isomers),decyl-dodecyl-phenoxyphenol (including isomers),decyl-dodecyl-cumyl-phenol (including isomers),decyl-phenyl-phenoxyphenol (including isomers),decyl-phenyl-cumyl-phenol (including isomers),dodecyl-phenyl-phenoxyphenol (including isomers),dodecyl-phenyl-cumyl-phenol (including isomers) andphenyl-phenoxy-cumyl-phenol (including isomers).

In addition, the standard boiling point of the monovalent aromatichydroxy compound is preferably lower than the standard boiling point ofthe divalent aromatic hydroxy compound produced according to the processof the present embodiment. Although there are cases on which amonovalent aromatic hydroxy compound having a standard boiling pointhigher than the standard boiling point of the divalent aromatic hydroxycompound can be used, in such cases, when the resulting isocyanatecompound and the divalent aromatic hydroxy compound are extracted from athermal decomposition reactor in the form of a gaseous phase componentin a carbamic acid ester thermal decomposition step to be describedlater, there is the risk of a polymeric polycarbamic acid ester, formedby an addition reaction between the isocyanate and the divalent aromatichydroxy compound, adhering to the walls of the reactor, thereby makingthis undesirable. There are no particular limitations on the combinationof the monovalent aromatic hydroxy compound and the divalent aromatichydroxy compound, and the combination thereof can be arbitrarilyselected.

There are no particular limitations on the reactor used in the reaction,and a known reactor can be used. For example, conventionally knownreactors such as a stirring tank, pressurized stirring tank, vacuumstirring tank or column reactor can be suitably combined and used. Thereare also no particular limitations on the material of the reactor, andknown materials can be used. Examples of materials that can be used mayinclude glass, stainless steel, carbon steel, Hastelloy, materialscomprising a base material lined with glass, and those provided with aTeflon coating. Since there are cases in which corrosion caused by theamine compound and/or aromatic hydroxy compound can become remarkabledepending on the step and conditions, in such cases, the reactor may bemade of glass, have a glass lining or have a Teflon coating, or aHastelloy reactors can be suitably selected.

The amine compound having primary amino groups is preferably supplied ina liquid form to the reactor where the reaction between the aromatichydroxy compound and the amine compound having primary amino groups iscarried out. In general, many of the previously listed examples of aminecompounds are solids at normal temperatures (for example, 20° C.), andalthough these amine compounds can be supplied in the liquid form byheating to a temperature higher than the melting point thereof, sincethere are cases in which side reactions such as a thermal denaturationreaction occurs due to heating if the amine compound is supplied at anexcessively high temperature, the amine compound is preferably suppliedin the liquid form at a comparatively low temperature as a mixture withthe above-mentioned aromatic hydroxy compound and water.

<Carbamic Acid Ester and Aromatic Hydroxy Compound Obtained by Reaction>

A mixture containing a carbamic acid ester and a compound having anaromatic hydroxyl group, which are originated from the aromaticpolycarbonate, is obtained by the reaction between the aromaticpolycarbonate resin and the amine compound having primary amino groupsas previously described. The following provides an explanation of thecarbamic acid ester and the compound having an aromatic hydroxyl group.

In the present embodiment, an aromatic polycarbonate compound is usedhaving a repetitive unit represented by the following formula (19):

(wherein Ar represents a divalent aromatic group having 6 to 20 carbonatoms, X represents a terminal end group in a form of a residue of achain terminator used when producing the aromatic polycarbonate, or ahydroxyl group, and k represents an integer of 0 or more); and

a compound represented by the following formula (20) is used for theamine compound having primary amino groups:

(wherein R¹ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms and aromatic groups having6 to 20 carbon atoms, the above groups contain an atom selected fromcarbon and oxygen atoms, and have an atomic number equal to n, and nrepresents an integer of from 2 to 10).

The compound having an aromatic hydroxyl group, which is originated fromthe aromatic polycarbonate obtained by carrying out the above reaction,is a compound represented by the following formula (21) having astructure in which a hydroxyl group (OH) is added to the Ar groupconstituting the main chain skeleton of the repetitive unit:

(wherein Ar represents a group as previously defined, Y represents aterminal end group X or —OH group as previously defined, and irepresents an integer of from 0 to k).

On the other hand, the carbamic acid ester originated from the aromaticpolycarbonate obtained by the above reaction is a compound representedby the following formula (22):

(wherein, Ar represents a group originated from the aromaticpolycarbonate as previously defined, R¹ represents a group originatedfrom the amine compound as previously defined, h represents an integerof from 0 to k, and n represents a value as previously defined).

In addition, in the reaction between the aromatic polycarbonate and theamine compound, in the case of using a monovalent aromatic hydroxycompound represented by the following formula (23) as previouslydescribed as a reaction solvent:

(wherein ring A represents an aromatic hydrocarbon ring which has 6 to20 carbon atoms and which may have a substituent, and the ring A may bea monocyclic or heterocyclic ring, and

R² represents an aliphatic group having 1 to 20 carbon atoms, analiphatic alkoxy group having 1 to 20 carbon atoms, an aryl group having6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, anaralkyl group having 7 to 20 carbon atoms or an aralkyloxy group having7 to 20 carbon atoms, the above groups contain an atom selected from thegroup consisting of carbon, oxygen and nitrogen atoms, and R² may alsobond with A to form a ring structure);

a transesterification reaction occurs between the aromatic polycarbonateand the monovalent aromatic hydroxy compound yielding a cleavagedproduct of the aromatic polycarbonate as represented by the followingformula (24) or formula (25):

(wherein Ar represents a group originated from the aromaticpolycarbonate as previously defined, A and R² represent groupsoriginated from the monovalent aromatic hydroxy compound as previouslydefined, X represents the terminal end group X or —OH group aspreviously defined, and g represents an integer of from 0 to k).

In such cases, a compound represented by the following formula (26) maybe contained in the form of a carbamic acid ester:

(wherein R¹ represents a group originated from the amine compound aspreviously defined, A and R² represent groups originated from themonovalent aromatic hydroxy compound as previously defined, X representsthe terminal end group X or —OH group as previously defined, frepresents an integer of from 0 to k, j represents an integer of from 1to n, and n represents a value as previously defined).

The following provides a more detailed explanation.

In the case of carrying out the reaction using the aromaticpolycarbonate in which the divalent aromatic hydroxy compoundrepresented by the structure Ar(OH)₂, in which two hydroxyl groups areadded to the Ar group in formula (19) above, is bisphenol A, and theterminal end group X is at least one group selected from the groupconsisting of a phenoxy group, p-tert-butylphenoxy group and hydroxylgroup, is used for the aromatic polycarbonate, and a divalent aminecompound represented by the following formula (27) is used for the aminecompound:

(wherein R³ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms and aromatic groups having6 to 20 carbon atoms, the above groups contain an atoms selected fromthe group consisting of carbon atoms and oxygen atoms);

a carbamic acid ester produced according to the process of the presentembodiment is a compound represented by the following formula (28):

(wherein R³ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms and aromatic groups having6 to 20 carbon atoms, the above groups contain an atom selected from thegroup consisting of carbon atoms and oxygen atoms, and each of R⁴ and R⁵independently represents a substituent selected from the grouprepresented by the following formula (29):

(wherein each of x, y and z independently represents an integer of 0 ormore).

The R³ in formula (29) above is a group originated from theabove-mentioned amine compound, and is preferably a group originatedfrom a linear hydrocarbon group such as methylene, dimethylene,trimethylene, tetramethylene, pentamethylene, hexamethylene oroctamethylene; unsubstituted acyclic hydrocarbon groups such ascyclopentane, cyclohexane, cycloheptane, cyclooctane orbis(cyclohexyl)alkane; alkyl-substituted cyclohexanes such asmethylcyclopentane, ethylcyclopentane, methylcyclohexane (includingisomers), ethylcyclohexane (including isomers), propylcyclohexane(including isomers), butylcyclohexane (including isomers),pentylcyclohexane (including isomers) or hexylcyclohexane (includingisomers); dialkyl-substituted cyclohexanes such as dimethylcyclohexane(including isomers), diethylcyclohexane (including isomers) ordibutylcyclohexane (including isomers); trialkyl-substitutedcyclohexanes such as 1,5,5-trimethylcyclohexane,1,5,5-triethylcyclohexane, 1,5,5-tripropylcyclohexane (includingisomers) or 1,5,5-tributylcyclohexane (including isomers);monoalkyl-substituted benzenes such as toluene, ethylbenzene orpropylbenzene; dialkyl-substituted benzenes such as xylene,diethylbenzene or dipropylbenzene; and aromatic hydrocarbons such asdiphenylalkane or benzene. Particularly preferable examples may includehexamethylene, phenylene, diphenylmethane, toluene, cyclohexane, xylene,methylcyclohexane, isophorone and cyclohexylmethane groups. Namely,groups originated from aliphatic diamines such as hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) (including isomers), cyclohexanediamine (including isomers) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (including isomers); and aromatic diamines such as phenylenediamine (including isomers), toluene diamine (including isomers) or4,4′-methylenedianiline (including isomers) are preferable, while groupsoriginated from aliphatic diamines such as hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) (including isomers), cyclohexanediamine (including isomers) or 3-aminomethyl-3,5,5-trimethylcyclohexylamine (including isomers) are particularly preferable, while groupsoriginated from hexamethylene diamine,4,4′-methylenebis(cyclohexylamine) or3-aminomethyl-3,5,5-trimethylcyclohexyl amine are more preferable.

The carbamic acid ester is preferably used as a raw material forproducing an isocyanate compound in particular. Although the detailsthereof will be described later, an isocyanate and divalent aromatichydroxy compound (bisphenol A) are formed by subjecting the carbamicacid ester to a thermal decomposition reaction. The bisphenol Aunexpectedly demonstrates the effect of improving the yield ofisocyanate by inhibiting thermal denaturation of the carbamic acid esterrepresented by formula (8) above. In addition, since the boiling pointof bisphenol A is higher than that of the isocyanate compound formed,the isocyanate can be recovered in the form of a gaseous phase componentwhile the bisphenol A can be recovered in the form of a liquid phasecomponent, thereby facilitating separation of the thermal decompositionproducts. Moreover, since the bisphenol A dissolves by-products from thethermal denaturation reaction as represented by, for example, theformulas (8) and/or (9) and/or (10) above attributable to the carbamicacid ester and/or the thermal decomposition product in the form of theisocyanate, by-products from the thermal denaturation reaction can beexpelled from the reactor where the thermal decomposition reaction iscarried out in the form of a solution of bisphenol A, thereby making itpossible to prevent adherence and accumulation on the walls of thereactor while also enabling operation of the isocyanate productionprocess based on a thermal decomposition reaction over a long period oftime.

<Transfer of Reaction Liquid>

The reaction liquid containing carbamic acid ester produced by theprocess according to the present embodiment is preferably removed fromthe reactor where the reaction was carried out and transferred to areaction where the thermal decomposition reaction is carried out on thecarbamic acid ester (to be referred to as “the thermal decompositionreactor”) followed by carrying out the thermal decomposition reaction onthe carbamic acid ester. In this manner, by using separator reactors forthe reactor where the carbamic acid ester is produced and the thermaldecomposition reactor, a suitable reactor can be selected for eachreaction and the reaction conditions can be flexibly set, thereby makingit possible to enhance the yield of each reaction.

Since these carbamic acid esters easily form intermolecular hydrogenbonds by bonding urethane constituting the carbamic acid esters, theyfrequently have a high melting point. In the transfer of such carbamicacid esters, for example, a solid carbamic acid ester can be transferredafter subjecting to excipiation treatment such as by crushing or forminginto pellets. However, in the case of transferring a solid carbamic acidester that has been subjected to excipiation treatment, there are manycases in which a complex apparatus for stably transferring a fixedamount of carbamic acid ester is required or a step is required forunifying the form of the carbamic acid ester within a certain range isrequired in cases of frequent clogging of the transfer line orvariations in the form of the carbamic acid ester. Thus, the carbamicacid ester is preferably supplied to the thermal decomposition reactorin a liquid form.

The method used to supply the carbamic acid ester to the thermaldecomposition reactor in the liquid form can preferably employ a methodin which it is supplied in the form of a reaction mixture obtained byreaction of the aromatic polycarbonate and the amine compound havingprimary amino groups.

The inventors of the present invention unexpectedly found that when thecarbamic acid ester is transferred in the form of a mixture with anaromatic hydroxy compound, reductions in carbamic acid ester caused bythermal denaturation of the carbamic acid ester and the like as well asdecreases in yield of the isocyanate compound can be inhibited. Althoughthe reason for demonstrating this effect is uncertain, the inventors ofthe present invention presumed that, in a reaction that forms urea bondsas represented by the formula (8) above, as a result of urethane bonds(—NHCOO—) of the carbamic acid ester and the aromatic hydroxy compoundcontained in the reaction mixture forming hydrogen bonds, since theurethane bonds are formed in a state in which it is difficult for themto approach each other, it is difficult for the reaction resulting inthe formation of urea bonds to occur.

There are no particular limitations on the method used to obtain amixture of the carbamic acid ester and the aromatic hydroxy compound,and for example, the carbamic acid ester obtained by the reactionbetween the aromatic polycarbonate and the amine compound having primaryamino groups as previously described may be separated and recovered bythe known method such as crystallization, distillative separation ormembrane separation followed by mixing the carbamic acid ester and thearomatic hydroxy compound. In addition, the aromatic hydroxy compoundmay be added and mixed with a mixture containing the carbamic acid esterobtained by reacting the aromatic polycarbonate and the amine compoundhaving primary amino groups.

Alternatively, a reaction mixture containing the carbamic acid ester andthe aromatic hydroxy compound, obtained by carrying out the reactionbetween the aromatic polycarbonate and the amine compound having primaryamino groups as described above using the aromatic hydroxy compound as areaction solvent, may be used directly. Since this method enables thereaction mixture to be transferred directly, the process is simplified,thereby making this more preferable.

The transfer of the mixture is preferably carried out within atemperature range of from 10° C. to 180° C., more preferably within arange of from 70° C. to 170° C. and even more preferably within a rangeof from 100° C. to 150° C. If the temperature is excessively high, theeffect of the aromatic hydroxy compound of inhibiting thermaldenaturation of the carbamic acid ester tends to be difficult to obtain,while on the other hand, if the temperature is excessively low, theviscosity of the mixture increases, which may cause problems duringtransfer.

<Thermal Decomposition of Carbamic Acid Ester>

The following provides an explanation of the production of theisocyanate and divalent aromatic hydroxy compound by thermaldecomposition of the carbamic acid ester.

The thermal decomposition reaction of the present embodiment is areaction for forming the corresponding isocyanate compound from thecarbamic acid ester. In particular, the divalent aromatic hydroxycompound is formed simultaneous to the isocyanate from a carbamic acidester in which h and g are both 0 in the above-mentioned formula (22) orformula (26).

The reaction temperature is generally within a range of from 100 to 300°C., and although a high temperature is preferable to increase thereaction rate, on the other hand, since there are cases in which sidereactions as previously described may be induced at high temperaturesdepending on the carbamic acid ester and/or product in the form of theisocyanate compound, the reaction temperature is preferably within arange of from 150 to 250° C. A known cooling apparatus or heatingapparatus may be installed to maintain a constant reaction temperature.In addition, although varying according to the types of compounds usedand the reaction temperature, the reaction pressure is such that thereaction may be carried out at decreased pressure, normal pressure orincreased pressure, and the reaction is generally carried out within arange of from 20 to 1×10⁶ Pa. There are no particular limitations on thereaction time (residence time in the case of a continuous process), andis generally within a range of from 0.001 to 100 hours, preferablywithin a range of from 0.005 to 50 hours and more preferably within arange of from 0.01 to 10 hours.

A catalyst is preferably not used in the present embodiment. Althoughthe thermal decomposition reaction may be promoted by using a catalyst,this is not preferable since there are many cases in which there isincreased susceptibility to the occurrence of side reactionsattributable to the carbamic acid ester and/or product isocyanatecompound as previously described.

The above-mentioned side reactions may occur in the case a carbamic acidester is held for a long time at a high temperature. In addition, theisocyanate compound formed by the thermal decomposition reaction mayalso cause side reactions as previously described. Thus, the time duringwhich the carbamic acid ester and the isocyanate compound are held at ahigh temperature is preferably as short as possible, and the thermaldecomposition reaction is preferably carried out with a continuousprocess. A continuous process refers to a process in which the mixturecontaining the carbamic acid ester is continuously supplied to thereactor and subjected to the thermal decomposition reaction, and theresulting isocyanate compound and divalent aromatic hydroxy compound arecontinuously extracted from the thermal decomposition reactor. In thiscontinuous process, low boiling point components formed by thermaldecomposition of carbamic acid ester are preferably recovered from thetop of the thermal decomposition reactor in the form of a gaseous phasecomponent, while the remainder is recovered from the bottom of thethermal decomposition reactor in the form of a liquid phase component.Here, low boiling point components include the isocyanate compoundand/or the reaction solvent in the form of the monovalent aromatichydroxy compound. Although all compounds present in the thermaldecomposition reactor can be recovered in the form of a gaseous phasecomponent, the presence of a liquid component in the thermaldecomposition reactor has the effect of preventing adherence andaccumulation of polymeric compounds on the thermal decomposition reactorby dissolving polymeric compounds formed by side reactions induced bythe carbamic acid ester and/or isocyanate compound. Although anisocyanate compound and divalent aromatic hydroxy compound are formed bythermal decomposition of the carbamic acid ester, at least one of thesecompounds is recovered in the form of a gaseous phase component.Although which of these compounds is recovered in the form of a gaseousphase component is dependent on the conditions of the thermaldecomposition reaction, from the viewpoint of obtaining a highly pureisocyanate compound, the isocyanate compound is preferably extracted inthe form of a gaseous phase component. In the case the carbamic acidester is subjected to the thermal decomposition reaction after beingsupplied to the thermal decomposition reactor in the form of a mixturewith the aromatic hydroxy compound as previously described, althoughwhether the aromatic hydroxy compound is recovered as a gaseous phasecomponent or a liquid phase component depends on the conditions of thethermal decomposition reaction, it is preferably recovered in the formof a gaseous phase component from the viewpoint of avoiding the carbamicacid ester being formed by reacting an isocyanate compound and thearomatic hydroxy compound, and the carbamic acid ester being recoveredtogether with the isocyanate.

For example, a method can be employed whereby the isocyanate compoundformed by the thermal decomposition reaction and the aromatic hydroxycompound are recovered in the form of a gaseous phase component, and aliquid component is recovered containing the divalent aromatic hydroxycompound and/or the carbamic acid ester. In this method, the isocyanatecompound and the aromatic hydroxy compound may also be recoveredseparately in the thermal decomposition reactor. The gaseous phasecomponent containing the recovered isocyanate compound is preferablysupplied to a distillation apparatus for separating and purifying theisocyanate compound in the gaseous phase. Although the gaseous phasecomponent containing the recovered isocyanate compound can be suppliedto a distillation apparatus after being transformed to the liquid phaseby a condenser and the like, there are many cases in which the apparatusbecomes complex and the amount of energy used increases, thereby makingthis undesirable. On the other hand, the liquid phase componentcontaining the divalent aromatic hydroxy compound and/or the carbamicacid ester is recovered from the bottom of the thermal decompositionreactor, and in the case the liquid phase component contains carbamicacid ester, all or a portion of the liquid phase component is suppliedto the top of the thermal decomposition reactor after which the carbamicacid ester is resubjected to the thermal decomposition reaction. The topof the thermal decomposition reactor as referred to here indicates, forexample, the level of the second plate or higher from the bottom interms of the number of theoretical plates in the case the thermaldecomposition reactor is a distillation column, and in the case thethermal decomposition reactor is a thin film distiller, indicates theportion higher than the heated transfer surface. When supplying all or aportion of the liquid phase component to the top of the thermaldecomposition reactor, the liquid phase component is transferred whilepreferably maintaining at 10 to 300° C., more preferably 30° C. to 250°C. and even more preferably 50° C. to 120° C. In addition, whenre-supplying all or a portion of the liquid phase component to thethermal decomposition reactor, this may be carried out after havingremoved all or a portion of the divalent aromatic hydroxy compoundcontained in the liquid phase component.

In addition, a method can also be employed whereby, for example, theisocyanate compound formed by the thermal decomposition reaction isrecovered in the form of a gaseous phase component, while a liquid phasecomponent is recovered containing the aromatic hydroxy compound,divalent aromatic hydroxy compound and/or carbamic acid ester. Thegaseous phase component containing the recovered isocyanate compound ispreferably supplied in the gaseous phase to a distillation apparatus forseparating and purifying the isocyanate. Although the gaseous phasecomponent containing the recovered isocyanate compound can be suppliedto a distillation apparatus after transforming to a liquid phase by acondenser and the like, there are many cases in which the apparatusbecomes complex and the amount of energy used increases, thereby makingthis undesirable. On the other hand, the liquid phase componentcontaining the aromatic hydroxy compound, divalent aromatic hydroxycompound and/or carbamic acid ester is recovered from the bottom of thethermal decomposition reactor, and in the case the liquid phasecomponent contains carbamic acid ester, all or a portion of the liquidphase component is preferably supplied to the top of the thermaldecomposition reactor after which the carbamic acid ester is resubjectedto the thermal decomposition reaction. When supplying all or a portionof the liquid phase component to the top of the thermal decompositionreactor, the liquid phase component is transferred while preferablymaintaining at 10° C. to 300° C., more preferably 30° C. to 250° C. andeven more preferably 50° C. to 120° C. In addition, when re-supplyingall or a portion of the liquid phase component to the thermaldecomposition reactor, this may be carried out after having removed allor a portion of the divalent aromatic hydroxy compound and afterremoving all or a portion of the aromatic hydroxy compound from theliquid phase component.

Although previously described, the liquid phase component is preferablyrecovered from the bottom of the thermal decomposition reactor in thethermal decomposition reaction. This is because, by allowing the liquidphase component to be present in the thermal decomposition reactor, theliquid phase component dissolves polymeric by-products formed by sidereactions induced by the carbamic acid ester and/or isocyanate, therebyenabling these by-products to be expelled from the thermal decompositionreactor in the form of a liquid phase component and resulting in theeffect of reducing adherence and accumulation of the polymeric compoundsin the thermal decomposition reactor.

In the case carbamic acid ester is contained in the liquid phasecomponent, although all or a portion of the liquid phase component issupplied to the top of the thermal decomposition reactor and thecarbamic acid ester is resubjected to the thermal decompositionreaction, repetition of this step may result in the accumulation ofpolymeric by-products in the liquid phase component. In such cases, allor a portion of the liquid phase component can be removed from thereaction system, thereby reducing accumulation of polymeric by-productsor maintaining at a fixed concentration thereof.

The aromatic hydroxy compound obtained in the above process can berecovered by separation and reused as a reaction solvent duringproduction of the carbamic acid ester and/or as a solvent used duringtransfer of the mixture containing the carbamic acid ester and/or as asolvent in the carbamic acid ester thermal decomposition reaction.

In addition, the isocyanate recovered by the above process can bepurified by the known method such as distillative separation or membraneseparation. In addition, the divalent aromatic hydroxy compoundrecovered after going through the above process can be purified by themethod such as distillative separation, film separation orcrystallization.

Although there are no particular limitations on the type of the thermaldecomposition reactor, the known distillation apparatus is usedpreferably in order to efficiency recover the gaseous phase component.Various known methods are used for such a reactor, examples of which mayinclude types using reactors containing a distillation column,multistage distillation column, multitubular reactor, continuousmultistage distillation column, packed column, thin film evaporator,reactor provided with a support inside, forced circulation reactor,falling film evaporator, falling drop evaporator, and types usingcombinations thereof. Methods using a tubular reactor are preferablefrom the viewpoint of rapidly removing low boiling point components fromthe reaction system, while a structure having a large gas-liquid contactarea is preferable for being able to rapidly transfer the low boilingpoint components formed to the gaseous phase.

Although the material of the thermal decomposition reactor and lines maybe any known material provided it does not have a detrimental effect onthe carbamic acid ester, divalent aromatic hydroxy compound orisocyanate and the like, materials such as SUS304, SUS316 or SUS316L areinexpensive and can therefore be used preferably.

<Cleaning of Thermal Decomposition Reactor>

In the present embodiment, there are cases in which the reaction liquidcontaining carbamic acid ester obtained by reacting the aromaticpolycarbonate and the amine compound having primary amino groupscontains polymeric side reaction products represented by, for example,the above-mentioned formula (8), (9) and (10). Since these side reactionproducts easily dissolve in the aromatic hydroxy compound in many cases,they are dissolved in the reaction liquid containing the aryl carbamate.However, if the majority of the aromatic hydroxy compound is extractedfrom the thermal decomposition reactor in the form of a gaseous phasecomponent, the side reaction products end up precipitating in thethermal decomposition reactor and frequency adhere thereto. When thesecompounds that have adhered to the thermal decomposition reactoraccumulated to a certain degree, they may impair operation of thethermal decomposition reactor and make long-term operation difficult,thereby resulting in the need to disassemble and clean the thermaldecomposition reactor.

The inventors of the present invention unexpectedly found that compoundadhered to the thermal decomposition reactor easily dissolve in anaromatic hydroxy compound. On the basis of this finding, in the caseside reaction product have adhered to the thermal decomposition reactor,the inventors of the present invention proposed and perfected a methodfor keeping the inside of the thermal decomposition reactor clean bycleaning the walls of the thermal decomposition reactor with an aromatichydroxy compound to dissolve these side reaction products and removethem from the thermal decomposition reactor. As a result of employingthis method, since the walls of the thermal decomposition reactor can becleaned without having to disassemble and separately clean the thermaldecomposition reactor, the downtime of the thermal decomposition reactorcan be minimized, thereby resulting in high isocyanate productionefficiency.

There are no particular limitations on the cleaning solvent provided itdissolves the polymeric by-products, and although an organic acid orinorganic acid may be used, organic acid is used preferably. Althoughexamples of organic acids may include carboxylic acid, sulfonic acid,sulfinic acid, phenols, enols, thiophenols, imides, oximes and aromaticsulfonamides, carboxylic acid and phenols are used preferably. Examplesof such compounds may include saturated or unsaturated aliphaticmonocarboxylic acids such as formic acid, acetic acid, propionic acid,n-butyric acid, isobutyric acid, valeric acid, isovaleric acid,2-methylbutanoic acid, pivalic acid, hexanoic acid, isocaproic acid,2-ethylbutanoic acid, 2,2-dimethylbutanoic acid, heptanoic acid(including isomers), octanoic acid (including isomers), nonanoic acid(including isomers), decanoic acid (including isomers), undecanoic acid(including isomers), dodecanoic acid (including isomers), tetradecanoicacid (including isomers), hexadecanoic acid (including isomers), acrylicacid, crotonic acid, isocrotonic acid, vinyl acetate, methacrylic acid,angelic acid, tiglic acid, allyl acetate or undecenoic acid (includingisomers); saturated or unsaturated aliphatic dicarboxylic acids such asoxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid,heptane diacid (including isomers), octane diacid (including isomers),nonane diacid (including isomers), decane diacid (including isomers),maleic acid, fumaric acid, methylmaleic acid, methylfumaric acid,pentene diacid (including isomers), itaconic acid or allylmalonic acid;saturated or unsaturated aliphatic tricarboxylic acids such as1,2,3-propane tricarboxylic acid, 1,2,3-propene tricarboxylic acid or2,3-dimethylbutane-1,2,3-tricarboxylic acid; aromatic carboxylic acidssuch as benzoic acid, methylbenzoic acid (including isomers),ethylbenzoic acid (including isomers), propyl benzoic acid (includingisomers), dimethylbenzoic acid (including isomers) or trimethylbenzoicacid (including isomers); aromatic dicarboxylic acids such as phthalicacid, isophthalic acid, terephthalic acid or methylisophthalic acid(including isomers); aromatic tricarboxylic acids such as hemimelliticacid, trimellitic acid or trimesinic acid; and aromatic hydroxycompounds such as phenol. Among these, aromatic hydroxy compounds arepreferable in consideration of the solubility of the polymericby-products and effects in the case of the cleaning solvent remaining inthe thermal decomposition reactor. Examples of such aromatic hydroxycompounds may include mono-substituted phenols such as phenol,methylphenol (including isomers), ethylphenol (including isomers),propylphenol (including isomers), butylphenol (including isomers),pentylphenol (including isomers), hexylphenol (including isomers),heptylphenol (including isomers), octylphenol (including isomers),nonylphenol (including isomers), decylphenol (including isomers),dodecylphenol (including isomers), phenylphenol (including isomers),phenoxyphenol (including isomers) or cumylphenol (including isomers);di-substituted phenols such as dimethylphenol (including isomers),diethylphenol (including isomers), dipropylphenol (including isomers),dibutylphenol (including isomers), dipentyphenol (including isomers),dihexylphenol (including isomers), diheptylphenol (including isomers),dioctylphenol (including isomers), dinonylphenol (including isomers),didecylphenol (including isomers), didodecylphenol (including isomers),diphenylphenol (including isomers), diphenoxyphenol (including isomers),dicumylphenol (including isomers), methylethylphenol (includingisomers), methylpropylphenol (including isomers), methylbutylphenol(including isomers), methylpentylphenol (including isomers),methylhexylphenol (including isomers), methylheptylphenol (includingisomers), methyloctylphenol (including isomers), methylnonylphenol(including isomers), methyldecylphenol (including isomers),methyldodecylphenol (including isomers), methylphenylphenol (includingisomers), methylphenoxyphenol (including isomers), methylcumylphenol(including isomers), ethylpropylphenol (including isomers),ethylbutylphenol (including isomers), ethylpentylphenol (includingisomers), ethylhexylphenol (including isomers), ethylheptylphenol(including isomers), ethyloctylphenol (including isomers),ethylnonylphenol (including isomers), ethyldecylphenol (includingisomers), ethyldodecylphenol (including isomers), ethylphenylphenol(including isomers), ethylphenoxyphenol (including isomers),ethylcumylphenol (including isomers), propylbutylphenol (includingisomers), propylpentylphenol (including isomers), propylhexylphenol(including isomers), propylheptylphenol (including isomers),propyloctylphenol (including isomers), propylnonylphenol (includingisomers), propyldecylphenol (including isomers), propyldodecylphenol(including isomers), propylphenylphenol (including isomers),propylphenoxyphenol (including isomers), propylcumylphenol (includingisomers), butylpentylphenol (including isomers), butylhexylphenol(including isomers), butylheptylphenol (including isomers),butyloctylphenol (including isomers), butylnonylphenol (includingisomers), butyldecylphenol (including isomers), butyldodecylphenol(including isomers), butylphenylphenol (including isomers),butylphenoxyphenol (including isomers), butylcumylphenol (includingisomers), pentylhexylphenol (including isomers), pentylheptylphenol(including isomers), pentyloctylphenol (including isomers),pentylnonylphenol (including isomers), pentyldecylphenol (includingisomers), pentyldodecylphenol (including isomers), pentylphenylphenol(including isomers), pentylphenoxyphenol (including isomers),pentylcumylphenol (including isomers), hexylheptylphenol (includingisomers), hexyloctylphenol (including isomers), hexylnonylphenol(including isomers), hexyldecylphenol (including isomers),hexyldodecylphenol (including isomers), hexylphenylphenol (includingisomers), hexylphenoxyphenol (including isomers), hexylcumylphenol(including isomers), heptyloctylphenol (including isomers),heptylnonylphenol (including isomers), heptyldecylphenol (includingisomers), heptyldodecylphenol (including isomers), heptylphenylphenol(including isomers), heptylphenoxyphenol (including isomers),heptylcumylphenol (including isomers), octylnonylphenol (includingisomers), octyldecylphenol (including isomers), octyldodecylphenol(including isomers), octylphenylphenol (including isomers),octylphenoxyphenol (including isomers), octylcumylphenol (includingisomers), nonyldecylphenol (including isomers), nonyldodecylphenol(including isomers), nonylphenylphenol (including isomers),nonylphenoxyphenol (including isomers), nonylcumylphenol (includingisomers), dodecylphenylphenol (including isomers), dodecylphenoxyphenol(including isomers) or dodecylcumylphenol (including isomers); andtri-substituted phenols such as trimethylphenol (including isomers),triethylphenol (including isomers), tripropylphenol (including isomers),tributylphenol (including isomers), tripentylphenol (including isomers),trihexylphenol (including isomers), triheptylphenol (including isomers),trioctylphenol (including isomers), trinonylphenol (including isomers),tridecylphenol (including isomers), tridodecylphenol (includingisomers), triphenylphenol (including isomers), triphenoxyphenol(including isomers), tricumylphenol (including isomers),dimethylethylphenol (including isomers), dimethylpropylphenol (includingisomers), dimethylbutylphenol (including isomers), dimethylpentylphenol(including isomers), dimethylhexylphenol (including isomers),dimethylheptylphenol (including isomers), dimethyloctylphenol (includingisomers), dimethylnonylphenol (including isomers), dimethyldecylphenol(including isomers), dimethyldodecylphenol (including isomers),dimethylphenylphenol (including isomers), dimethylphenoxyphenol(including isomers), dimethylcumylphenol (including isomers),diethylmethylphenol (including isomers), diethylpropylphenol (includingisomers), diethylbutylphenol (including isomers), diethylpentylphenol(including isomers), diethylhexylphenol (including isomers),diethylheptylphenol (including isomers), diethyloctylphenol (includingisomers), diethylnonylphenol (including isomers), diethyldecylphenol(including isomers), diethyldodecylphenol (including isomers),diethylphenylphenol (including isomers), diethylphenoxyphenol (includingisomers), diethylcumylphenol (including isomers), dipropylmethylphenol(including isomers), dipropylethylphenol (including isomers),dipropylbutylphenol (including isomers), dipropylpentylphenol (includingisomers), dipropylhexylphenol (including isomers), dipropylheptylphenol(including isomers), dipropyloctylphenol (including isomers),dipropylnonylphenol (including isomers), dipropyldecylphenol (includingisomers), dipropyldodecylphenol (including isomers),dipropylphenylphenol (including isomers), dipropylphenoxyphenol(including isomers), dipropylcumylphenol (including isomers),dibutylmethylphenol (including isomers), dibutylethylphenol (includingisomers), dibutylpropylphenol (including isomers), dibutylpentylphenol(including isomers), dibutylhexylphenol (including isomers),dibutylheptylphenol (including isomers), dibutyloctylphenol (includingisomers), dibutylnonylphenol (including isomers), dibutyldecylphenol(including isomers), dibutyldodecylphenol (including isomers),dibutylphenylphenol (including isomers), dibutylphenoxyphenol (includingisomers), dibutylcumylphenol (including isomers), dipentylmethylphenol(including isomers), dipentylethylphenol (including isomers),dipentylpropylphenol (including isomers), dipentylbutylphenol (includingisomers), dipentylhexylphenol (including isomers), dipentylheptylphenol(including isomers), dipentyloctylphenol (including isomers),dipentylnonylphenol (including isomers), dipentyldecylphenol (includingisomers), dipentyldodecylphenol (including isomers),dipentylphenylphenol (including isomers), dipentylphenoxyphenol(including isomers), dipentylcumylphenol (including isomers),dihexylmethylphenol (including isomers), dihexylethylphenol (includingisomers), dihexylpropylphenol (including isomers), dihexylbutylphenol(including isomers), dihexylpentylphenol (including isomers),dihexylheptylphenol (including isomers), dihexyloctylphenol (includingisomers), dihexylnonylphenol (including isomers), dihexyldecylphenol(including isomers), dihexyldodecylphenol (including isomers),dihexylphenylphenol (including isomers), dihexylphenoxyphenol (includingisomers), dihexylcumylphenol (including isomers), diheptylmethylphenol(including isomers), diheptylethylphenol (including isomers),diheptylpropylphenol (including isomers), diheptylbutylphenol (includingisomers), diheptylpentylphenol (including isomers), diheptylhexylphenol(including isomers), diheptyloctylphenol (including isomers),diheptylnonylphenol (including isomers), diheptyldecylphenol (includingisomers), diheptyldodecylphenol (including isomers),diheptylphenylphenol (including isomers), diheptylphenoxyphenol(including isomers), diheptylcumylphenol (including isomers),dioctylmethylphenol (including isomers), dioctylethylphenol (includingisomers), dioctylpropylphenol (including isomers), dioctylbutylphenol(including isomers), dioctylpentylphenol (including isomers),dioctylhexylphenol (including isomers), dioctylheptylphenol (includingisomers), dioctylnonylphenol (including isomers), dioctyldecylphenol(including isomers), dioctyldodecylphenol (including isomers),dioctylphenylphenol (including isomers), dioctylphenoxyphenol (includingisomers), dioctylcumylphenol (including isomers), dinonylmethylphenol(including isomers), dinonylethylphenol (including isomers),dinonylpropylphenol (including isomers), dinonylbutylphenol (includingisomers), dinonylpentylphenol (including isomers), dinonylhexylphenol(including isomers), dinonylheptylphenol (including isomers),dinonyloctylphenol (including isomers), dinonyldecylphenol (includingisomers), dinonyldodecylphenol (including isomers), dinonylphenylphenol(including isomers), dinonylphenoxyphenol (including isomers),dinonylcumylphenol (including isomers), didecylmethylphenol (includingisomers), didecylethylphenol (including isomers), didecylpropylphenol(including isomers), didecylbutylphenol (including isomers),didecylpentylphenol (including isomers), didecylhexylphenol (includingisomers), didecylheptylphenol (including isomers), didecyloctylphenol(including isomers), didecylnonylphenol (including isomers),didecyldodecylphenol (including isomers), didecylphenylphenol (includingisomers), didecylphenoxyphenol (including isomers), didecylcumylphenol(including isomers), didodecylmethylphenol (including isomers),didodecylethylphenol (including isomers), didodecylpropylphenol(including isomers), didodecylbutylphenol (including isomers),didodecylpentylphenol (including isomers), didodecylhexylphenol(including isomers), didodecylheptylphenol (including isomers),didodecyloctylphenol (including isomers), didodecylnonylphenol(including isomers), didodecyldecylphenol (including isomers),didodecyldodecylphenol (including isomers), didodecylphenylphenol(including isomers), didodecylphenoxyphenol (including isomers),didodecylcumylphenol (including isomers), diphenylmethylphenol(including isomers), diphenylethylphenol (including isomers),diphenylpropylphenol (including isomers), diphenylbutylphenol (includingisomers), diphenylpentylphenol (including isomers), diphenylhexylphenol(including isomers), diphenylheptylphenol (including isomers),diphenyloctylphenol (including isomers), diphenylnonylphenol (includingisomers), diphenyldecylphenol (including isomers), diphenyldodecylphenol(including isomers), diphenylphenoxyphenol (including isomers),diphenylcumylphenol (including isomers), diphenoxymethylphenol(including isomers), diphenoxyethylphenol (including isomers),diphenoxypropylphenol (including isomers), diphenoxybutylphenol(including isomers), diphenoxypentylphenol (including isomers),diphenoxyhexylphenol (including isomers), diphenoxyheptylphenol(including isomers), diphenoxyoctylphenol (including isomers),diphenoxynonylphenol (including isomers), diphenoxydecylphenol(including isomers), diphenoxydodecylphenol (including isomers),diphenoxyphenylphenol (including isomers), diphenoxycumylphenol(including isomers), dicumylmethylphenol (including isomers),dicumylethylphenol (including isomers), dicumylpropylphenol (includingisomers), dicumylbutylphenol (including isomers), dicumylpentylphenol(including isomers), dicumylhexylphenol (including isomers),dicumylheptylphenol (including isomers), dicumyloctylphenol (includingisomers), dicumylnonylphenol (including isomers), dicumyldecylphenol(including isomers), dicumyldodecylphenol (including isomers),dicumylphenylphenol (including isomers), dicumylphenoxyphenol (includingisomers), methylethylpropylphenol (including isomers),methylethylbutylphenol (including isomers), methylethylpentylphenol(including isomers), methylethylhexylphenol (including isomers),methylethylheptylphenol (including isomers), methylethyloctylphenol(including isomers), methylethylnonylphenol (including isomers),methylethyldecylphenol (including isomers), methylethyldodecylphenol(including isomers), methylethylphenylphenol (including isomers),methylethylphenoxyphenol (including isomers), methylethylcumylphenol(including isomers), methylpropylbutylphenol (including isomers),methylpropylpentylphenol (including isomers), methylpropylhexylphenol(including isomers), methypropylheptylphenol (including isomers),methylpropyloctylphenol (including isomers), methylpropylnonylphenol(including isomers), methylpropyldecylphenol (including isomers),methylpropyldodecylphenol (including isomers), methylpropylphenylphenol(including isomers), methylpropylphenoxyphenol (including isomers),methylpropylcumylphenol (including isomers), methylbutylpentylphenol(including isomers), methylbutylhexylphenol (including isomers),methylbutylheptylphenol (including isomers), methylbutyloctylphenol(including isomers), methylbutylnonylphenol (including isomers),methylbutyldecylphenol (including isomers), methylbutyldodecylphenol(including isomers), methylbutylphenylphenol (including isomers),methylbutylphenoxyphenol (including isomers), methylbutylcumylphenol(including isomers), methylpentylhexylphenol (including isomers),methypentylheptylphenol (including isomers), methylpentyloctylphenol(including isomers), methylpentylnonylphenol (including isomers),methylpentyldecylphenol (including isomers), methylpentyldodecylphenol(including isomers), methylpentylphenylphenol (including isomers),methylpentylphenoxyphenol (including isomers), methylpentylcumylphenol(including isomers), methyhexylheptylphenol (including isomers),methylhexyloctylphenol (including isomers), methylhexylnonylphenol(including isomers), methylhexyldecylphenol (including isomers),methylhexyldodecylphenol (including isomers), methylhexylphenylphenol(including isomers), methylhexylphenoxyphenol (including isomers),methylhexylcumylphenol (including isomers), ethylpropylbutylphenol(including isomers), ethylpropylpentylphenol (including isomers),ethylpropylhexylphenol (including isomers), ethylpropylheptylphenol(including isomers), ethylpropyloctylphenol (including isomers),ethylpropylnonylphenol (including isomers), ethylpropyldecylphenol(including isomers), ethylpropyldodecylphenol (including isomers),ethylpropylphenylphenol (including isomers), ethylpropylphenoxyphenol(including isomers), ethylpropylcumylphenol (including isomers),ethylbutylphenol (including isomers), ethylbutylpentylphenol (includingisomers), ethylbutylhexylphenol (including isomers),ethylbutylheptylphenol (including isomers), ethylbutyloctylphenol(including isomers), ethylbutylnonylphenol (including isomers),ethylbutyldecylphenol (including isomers), ethylbutyldodecylphenol(including isomers), ethylbutylphenylphenol (including isomers),ethylbutylphenoxyphenol (including isomers), ethylbutylcumylphenol(including isomers), ethylpentylhexylphenol (including isomers),ethylpentylheptylphenol (including isomers), ethylpentyloctylphenol(including isomers), ethylpentylnonylphenol (including isomers),ethylpentyldecylphenol (including isomers), ethylpentyldodecylphenol(including isomers), ethylpentylphenylphenol (including isomers),ethylpentylphenoxyphenol (including isomers), ethylpentylcumylphenol(including isomers), ethylhexylheptylphenol (including isomers),ethylhexyloctylphenol (including isomers), ethylhexylnonylphenol(including isomers), ethylhexyldecylphenol (including isomers),ethylhexyldodecylphenol (including isomers), ethylhexylphenylphenol(including isomers), ethylhexylphenoxyphenol (including isomers),ethylhexylcumylphenol (including isomers), ethylheptyloctylphenol(including isomers), ethylheptylnonylphenol (including isomers),ethylheptyldecylphenol (including isomers), ethylheptyldodecylphenol(including isomers), ethylheptylphenylphenol (including isomers),ethylheptylphenoxyphenol (including isomers), ethylheptylcumylphenol(including isomers), ethyloctylnonylphenol (including isomers),ethyloctyldecylphenol (including isomers), ethyloctyldodecylphenol(including isomers), ethyloctylphenylphenol (including isomers),ethyloctylphenoxyphenol (including isomers), ethyloctylcumylphenol(including isomers), ethylnonyldecylphenol (including isomers),ethylnonyldodecylphenol (including isomers), ethylnonylphenylphenol(including isomers), ethylnonylphenoxyphenol (including isomers),ethylnonylcumylphenol (including isomers), ethyldecyldodecylphenol(including isomers), ethyldecylphenylphenol (including isomers),ethyldecylphenoxyphenol (including isomers), ethyldecylcumylphenol(including isomers), ethyldodecylphenylphenol (including isomers),ethyldodecylphenoxyphenol (including isomers), ethyldodecylcumylphenol(including isomers), ethylphenylphenoxyphenol (including isomers),ethylphenylcumylphenol (including isomers), propylbutylphenol (includingisomers), propylbutylpentylphenol (including isomers),propylbutylhexylphenol (including isomers), propylbutylheptylphenol(including isomers), propylbutyloctylphenol (including isomers),propylbutylnonylphenol (including isomers), propylbutyldecylphenol(including isomers), propylbutyldodecylphenol (including isomers),propylbutylphenylphenol (including isomers), propylbutylphenoxyphenol(including isomers), propylbutylcumylphenol (including isomers),propylpentylphenol (including isomers), propylpentylhexylphenol(including isomers), propylpentylheptylphenol (including isomers),propylpentyloctylphenol (including isomers), propylpentylnonylphenol(including isomers), propylpentyldecylphenol (including isomers),propylpentyldodecylphenol (including isomers), propylpentylphenylphenol(including isomers), propylpentylphenoxyphenol (including isomers),propylpentylcumylphenol (including isomers), propyl-hexyl-phenol(including isomers), propylhexylheptylphenol (including isomers),propylhexyloctylphenol (including isomers), propylhexylnonylphenol(including isomers), propylhexyldecylphenol (including isomers),propylhexyldodecylphenol (including isomers), propylhexylphenylphenol(including isomers), propylhexylphenoxyphenol (including isomers),propylhexylcumylphenol (including isomers), propylheptyloctylphenol(including isomers), propylheptylnonylphenol (including isomers),propylheptyldecylphenol (including isomers), propylheptyldodecylphenol(including isomers), propylheptylphenylphenol (including isomers),propylheptylphenoxyphenol (including isomers), propylheptylcumylphenol(including isomers), propyloctylnonylphenol (including isomers),propyloctyldecylphenol (including isomers), propyloctyldodecylphenol(including isomers), propyloctylphenylphenol (including isomers),propyloctylphenoxyphenol (including isomers), propyloctylcumylphenol(including isomers), propylnonyldecylphenol (including isomers),propylnonyldodecylphenol (including isomers), propylnonylphenylphenol(including isomers), propylnonylphenoxyphenol (including isomers),propylnonylcumylphenol (including isomers), propyldecyldodecylphenol(including isomers), propyldecylphenylphenol (including isomers),propyldecylphenoxyphenol (including isomers), propyldecylcumylphenol(including isomers), propyldodecylphenylphenol (including isomers),propyldodecylphenoxyphenol (including isomers), propyldodecylcumylphenol(including isomers), methylphenol (including isomers), ethylphenol(including isomers), propylphenol (including isomers), butylphenol(including isomers), pentylphenol (including isomers), hexylphenol(including isomers), heptylphenol (including isomers), octylphenol(including isomers), nonylphenol (including isomers), decylphenol(including isomers), dodecylphenol (including isomers), phenylphenol(including isomers), phenoxyphenol (including isomers) cumylphenol(including isomers) propylphenylphenoxyphenol (including isomers),propylphenylcumylphenol (including isomers), propylphenoxycumylphenol(including isomers), propyl-butyl-pentyl-phenol (including isomers),propyl-butyl-hexyl-phenol (including isomers),propyl-butyl-heptyl-phenol (including isomers),propyl-butyl-octyl-phenol (including isomers), propyl-butyl-nonyl-phenol(including isomers), propyl-butyl-decyl-phenol (including isomers),propyl-butyl-dodecyl-phenol (including isomers),propyl-butyl-phenyl-phenol (including isomers),propyl-butyl-phenoxyphenol (including isomers),propyl-butyl-cumyl-phenol (including isomers), propyl-pentyl-phenol(including isomers), propyl-pentyl-hexyl-phenol (including isomers),propyl-pentyl-heptyl-phenol (including isomers),propyl-pentyl-octyl-phenol (including isomers),propyl-pentyl-nonyl-phenol (including isomers),propyl-pentyl-decyl-phenol (including isomers),propyl-pentyl-dodecyl-phenol (including isomers),propyl-pentyl-phenyl-phenol (including isomers),propyl-pentyl-phenoxyphenol (including isomers),propyl-pentyl-cumyl-phenol (including isomers),propyl-hexyl-heptyl-phenol (including isomers),propyl-hexyl-octyl-phenol (including isomers), propyl-hexyl-nonyl-phenol(including isomers), propyl-hexyl-decyl-phenol (including isomers),propyl-hexyl-dodecyl-phenol (including isomers),propyl-hexyl-phenyl-phenol (including isomers),propyl-hexyl-phenoxyphenol (including isomers),propyl-hexyl-cumyl-phenol (including isomers),propyl-heptyl-octyl-phenol (including isomers),propyl-heptyl-nonyl-phenol (including isomers),propyl-heptyl-decyl-phenol (including isomers),propyl-heptyl-dodecyl-phenol (including isomers),propyl-heptyl-phenyl-phenol (including isomers),propyl-heptyl-phenoxyphenol (including isomers),propyl-heptyl-cumyl-phenol (including isomers),propyl-octyl-nonyl-phenol (including isomers), propyl-octyl-decyl-phenol(including isomers), propyl-octyl-dodecyl-phenol (including isomers),propyl-octyl-phenyl-phenol (including isomers),propyl-octyl-phenoxyphenol (including isomers),propyl-octyl-cumyl-phenol (including isomers), propyl-nonyl-decyl-phenol(including isomers), propyl-nonyl-dodecyl-phenol (including isomers),propyl-nonyl-phenyl-phenol (including isomers),propyl-nonyl-phenoxyphenol (including isomers),propyl-nonyl-cumyl-phenol (including isomers),propyl-decyl-dodecyl-phenol (including isomers),propyl-decyl-phenyl-phenol (including isomers),propyl-decyl-phenoxyphenol (including isomers),propyl-decyl-cumyl-phenol (including isomers),propyl-dodecyl-phenyl-phenol (including isomers),propyl-dodecyl-phenoxyphenol (including isomers), cumyl-phenol(including isomers) propyl-phenyl-phenoxyphenol (including isomers),propyl-phenyl-cumyl-phenol (including isomers), butylpentylhexylphenol(including isomers), butylpentylheptylphenol (including isomers),butylpentyloctylphenol (including isomers), butylpentylnonylphenol(including isomers), butylpentyldecylphenol (including isomers),butylpentyldodecylphenol (including isomers), butylpentylphenylphenol(including isomers), butylpentylphenoxyphenol (including isomers),butylpentylcumylphenol (including isomers), butylhexylheptylphenol(including isomers), butylhexyloctylphenol (including isomers),butylhexylnonylphenol (including isomers), butylhexyldecylphenol(including isomers), butylhexyldodecylphenol (including isomers),butylhexylphenylphenol (including isomers), butylhexylphenoxyphenol(including isomers), butylhexylcumylphenol (including isomers),butylheptyloctylphenol (including isomers), butylheptylnonylphenol(including isomers), butylheptyldecylphenol (including isomers),butylheptyldodecylphenol (including isomers), butylheptylphenylphenol(including isomers), butylheptylphenoxyphenol (including isomers),butylheptylcumylphenol (including isomers), butyloctylnonylphenol(including isomers), butyloctyldecylphenol (including isomers),butyloctyldodecylphenol (including isomers), butyloctylphenylphenol(including isomers), butyloctylphenoxyphenol (including isomers),butyloctylcumylphenol (including isomers), butylnonyldecylphenol(including isomers), butylnonyldodecylphenol (including isomers),butylnonylphenylphenol (including isomers), butylnonylphenoxyphenol(including isomers), butylnonylcumylphenol (including isomers),butyldecyldodecylphenol (including isomers), butyldecylphenylphenol(including isomers), butyldecylphenoxyphenol (including isomers),butyldecylcumylphenol (including isomers), butyldodecylphenol (includingisomers), butyldodecylphenylphenol (including isomers),butyldodecylphenoxyphenol (including isomers), butyldodecylcumylphenol(including isomers), butylphenylphenol (including isomers),butylphenylphenoxyphenol (including isomers), butylphenylcumylphenol(including isomers), pentylhexylheptylphenol (including isomers),pentylhexyloctylphenol (including isomers), pentylhexylnonylphenol(including isomers), pentylhexyldecylphenol (including isomers),pentylhexyldodecylphenol (including isomers), pentylhexylphenylphenol(including isomers), pentylhexylphenoxyphenol (including isomers),pentylhexylcumylphenol (including isomers), pentylheptyloctylphenol(including isomers), pentylheptylnonylphenol (including isomers),pentylheptyldecylphenol (including isomers), pentylheptyldodecylphenol(including isomers), pentylheptylphenylphenol (including isomers),pentylheptylphenoxyphenol (including isomers), pentylheptylcumylphenol(including isomers), pentyloctylnonylphenol (including isomers),pentyloctyldecylphenol (including isomers), pentyloctyldodecylphenol(including isomers), pentyloctylphenylphenol (including isomers),pentyloctylphenoxyphenol (including isomers), pentyloctylcumylphenol(including isomers), pentylnonyldecylphenol (including isomers),pentylnonyldodecylphenol (including isomers), pentylnonylphenylphenol(including isomers), pentylnonylphenoxyphenol (including isomers),pentylnonylcumylphenol (including isomers), pentyldecyldodecylphenol(including isomers), pentyldecylphenylphenol (including isomers),pentyldecylphenoxyphenol (including isomers), pentyldecylcumylphenol(including isomers), pentyldecyldodecylphenol (including isomers),pentyldecylphenylphenol (including isomers), pentyldecylphenoxyphenol(including isomers), pentyldecylcumylphenol (including isomers),pentyldodecylphenylphenol (including isomers),pentyldodecylphenoxyphenol (including isomers), pentyldodecylcumylphenol(including isomers), pentylphenylphenoxyphenol (including isomers),pentylphenylcumylphenol (including isomers), hexylheptyloctylphenol(including isomers), hexylheptylnonylphenol (including isomers),hexylheptyldecylphenol (including isomers), hexylheptyldodecylphenol(including isomers), hexylheptylphenylphenol (including isomers),hexylheptylphenoxyphenol (including isomers), hexylheptylcumylphenol(including isomers), hexyloctylnonylphenol (including isomers),hexyloctyldecylphenol (including isomers), hexyloctyldodecylphenol(including isomers), hexyloctylphenylphenol (including isomers),hexyloctylphenoxyphenol (including isomers), hexyloctylcumylphenol(including isomers), hexylnonyldecylphenol (including isomers),hexylnonyldodecylphenol (including isomers), hexylnonylphenylphenol(including isomers), hexylnonylphenoxyphenol (including isomers),hexyldecyldodecylphenol (including isomers), hexyldecylphenylphenol(including isomers), hexyldecylphenoxyphenol (including isomers),hexyldecylcumylphenol (including isomers), hexyldodecylphenylphenol(including isomers), hexyldodecylphenoxyphenol (including isomers),hexyldodecylcumylphenol (including isomers), hexylphenylphenoxyphenol(including isomers), hexylphenylcumylphenol (including isomers),heptyloctylnonylphenol (including isomers), heptyloctyldecylphenol(including isomers), heptyloctyldodecylphenol (including isomers),heptyloctylphenylhenol (including isomers), heptyloctylphenoxyphenol(including isomers), heptyloctylcumylphenol (including isomers),heptylnonyldecylphenol (including isomers), heptylnonyldodecylphenol(including isomers), heptylnonylphenylhenol (including isomers),heptylnonylphenoxyphenol (including isomers), heptylnonylcumylphenol(including isomers), heptyldecyldodecylphenol (including isomers),heptyldecylphenylphenol (including isomers), heptyldecylphenoxyphenol(including isomers), heptyldecylcumylphenol (including isomers),heptyldodecylphenylhenol (including isomers), heptyldodecylphenoxyphenol(including isomers), heptyldodecylcumylphenol (including isomers),heptylphenylphenoxyphenol (including isomers), heptylphenylcumylphenol(including isomers), octylnonyldecylphenol (including isomers),octylnonyldodecylphenol (including isomers), octylnonylphenylphenol(including isomers), octylnonylphenoxyphenol (including isomers),octylnonylcumylphenol (including isomers), octyldecyldodecylphenol(including isomers), octyldecylphenylphenol (including isomers),octyldecylphenoxyphenol (including isomers), octyldecylcumylphenol(including isomers), octyldodecylphenylphenol (including isomers),octyldodecylphenoxyphenol (including isomers), octyldodecylcumylphenol(including isomers), octyldodecylphenylphenol (including isomers),octyldodecylphenoxyphenol (including isomers), octyldodecylcumylphenol(including isomers), octylphenylphenoxyphenol (including isomers),octylphenylcumylphenol (including isomers), nonyldecyldodecylphenol(including isomers), nonyldecylphenylphenol (including isomers),nonyldecylphenoxyphenol (including isomers), nonyldecylcumylphenol(including isomers), nonyldodecylphenylphenol (including isomers),nonyldodecylphenoxyphenol (including isomers), nonyldodecylcumylphenol(including isomers), nonylphenylphenoxyphenol (including isomers),nonylphenylcumylphenol (including isomers), decyldoceylphenylphenol(including isomers), decyldodecylphenoxyphenol (including isomers),decyldodecylcumylphenol (including isomers), dodecylphenylphenoxyphenol(including isomers), dodecylphenylcumylphenol (including isomers) orphenylphenoxycumylphenol (including isomers). Among these aromatichydroxy compounds, a compound of the same type as the aromatic hydroxycompound used in the reaction between the aromatic polycarbonate and theamine compound having primary amino groups is more preferable inconsideration of the case of the cleaning solvent remaining aftercleaning the thermal decomposition reactor.

Various methods can be used to clean the thermal decomposition reactorusing the cleaning solvents listed above, examples of which may includea method whereby the thermal decomposition reactor is cleaned byintroducing cleaning solvent from the top of the thermal decompositionreactor, and a method whereby the inside of the thermal decompositionreactor is cleaned by introducing cleaning solvent into the bottom ofthe thermal decomposition reactor and heating up the cleaning solventinside the thermal decomposition reactor.

There are no particular limitations on the frequency at which cleaningis carried out, and the cleaning frequency can be arbitrarily determinedaccording to the compounds used, operating rate and the like. Thethermal decomposition reactor may also be provided with a line forintroducing cleaning solvent in the thermal decomposition reactor.

In addition, when carrying out thermal decomposition of carbamic acidester, the above-mentioned cleaning solvent can also be made to bepresent under the conditions of the thermal decomposition reaction forthe purpose of cleaning the thermal decomposition reactor. This differsfrom the inert solvent as referred to in the prior art (see, forexample, U.S. Pat. No. 4,081,472). For example, according to this patentdocument, although an inert solvent refers to a compound that does notreact with isocyanate formed by thermal decomposition of carbamic acidester, in contrast, as described in, for example, the Journal of theAmerican Chemical Society, Vol. 64, p. 2229, 1942 that urethane isformed by the reaction of an aromatic hydroxy compound and phenylisocyanate, aromatic hydroxy compounds are able to react withisocyanates. The aromatic hydroxy compound may be supplied to thethermal decomposition reactor after mixing when transferring thereaction mixture obtained by a reaction between diaryl carbonate and anamine compound to the thermal decomposition reactor, or may be suppliedby providing a line for supplying the aromatic hydroxy compound separatefrom the line for supplying the reaction mixture.

The carbamic acid ester obtained in the process of the presentembodiment is preferable as a raw material for producing isocyanatewithout using extremely toxic phosgene, and isocyanate obtained with theprocess of the present embodiment can be preferably used as a rawmaterial for the production of polyurethane foam, paints, adhesives andthe like. In addition, the divalent aromatic hydroxy compound obtainedin the process of the present embodiment can be preferably used as a rawmaterial for the production of aromatic polycarbonates. The process ofthe present embodiment also demonstrates the aspect of chemicalrecycling of aromatic polycarbonates. On the basis of the above, thepresent invention is industrially extremely important.

EXAMPLES

Although the following provides a detailed explanation of the presentinvention based on examples thereof, the scope of the present inventionis not limited by these examples.

<Analytical Methods>

1) NMR Analysis

Apparatus: JNM-A400 FT-NMR system, JEOL Ltd., Japan

(1) Preparation of ¹H and ¹³C-NMR Analysis Samples

About 0.3 g of sample solution were weighed followed by the addition ofabout 0.7 g of heavy chloroform (99.8%, Aldrich Corp., USA) and about0.05 g of internal standard in the form of tetramethyl tin (guaranteedreagent, Wako Pure Chemical Industries, Ltd., Japan) and mixing touniformity to obtain solutions used as NMR analysis samples.

(2) Quantitative Analysis

Analyses were performed on each standard and quantitative analyses wereperformed on the analysis sample solutions based on the resultingcalibration curve.

2) Liquid Chromatography

Apparatus: LC-10AT system, Shimadzu Corp., Japan

Column: Silica-60 column, Tosoh Corp., Japan, two columns connected inseries

Developing solvent: Mixed liquid of hexane/tetrahydrofuran (80/20) (v/v)

Solvent flow rate: 2 mL/min

Column temperature: 35° C.

Detector: R.I. (refractometer)

(1) Liquid Chromatography Analysis Samples

About 0.1 g of sample were weighed followed by the addition of about 1 gof tetrahydrofuran (dehydrated, Wako Pure Chemical Industries, Ltd.,Japan) and about 0.02 g of internal standard in the form of bisphenol A(guaranteed reagent, Wako Pure Chemical Industries, Ltd., Japan) andmixing to uniformity to obtain solutions used as liquid chromatographyanalysis samples.

(2) Quantitative Analysis

Analyses were performed on each standard and quantitative analyses wereperformed on the analysis sample solutions based on the resultingcalibration curve.

3) Gas Chromatography

Apparatus: GC-2010, Shimadzu Corp., Japan

Column: DB-1 column, Agilent Technologies Corp., USA, length: 30 m,inner diameter: 0.250 mm, film thickness: 1.00 μm

Column temperature: Held at 50° C. for 5 minutes followed by increasingat the rate of 10° C./min to 200° C.; held at 200° C. for 5 minutesfollowed by increasing at the rate of 10° C./min to 300° C.

Detector: FID

(1) Gas Chromatography Analysis Samples

About 0.05 g of sample were weighed followed by the addition of about 1g of toluene (dehydrated, Wako Pure Chemical Industries, Ltd., Japan)and about 0.02 g of internal standard in the form of diphenyl ether(Tokyo Chemical Industry Co., Ltd., Japan) and mixing to uniformity toobtain solutions used as gas chromatography analysis samples.

(2) Quantitative Analysis

Analyses were performed on each standard and quantitative analyses wereperformed on the analysis sample solutions based on the resultingcalibration curve.

Example 1

Step (1-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared using an apparatus like that shown in FIG. 1.

20.6 kg (100 mol) of molten 4-t-octylphenol (Tokyo Chemical IndustryCo., Ltd., Japan) were transferred from a storage tank 101 to a reactor102 heated to 200° C. after replacing the inside thereof with nitrogenwith a line 12 closed. 14.3 kg of bisphenol A polycarbonate (AldrichCorp., USA, weight average molecular weight: 65,000) were loaded intothe reactor 102 from a storage tank 100 and stirred. After confirmingthat the bisphenol A polycarbonate had dissolved, line 12 was opened andthe mixture was transferred to a storage tank 103.

Step (1-2): Production of Carbamic Acid Ester

A reaction was carried out using an apparatus like that shown in FIG. 2.

In a state where a line 23 was closed, the mixture produced in step(1-1) was supplied at a rate of 4.15 kg/hr via a line 21 from storagetank 103 to a baffled SUS reactor 202 maintained at about 150° C. afterreplacing the inside thereof with nitrogen. Hexamethylene diamine(Aldrich Corp., USA) was supplied at a rate of about 0.24 kg/hr via aline 22 from a storage tank 201 to the reactor 202. After analyzing thereaction liquid by gas chromatography and confirming that hexamethylenediamine was no longer detected, the line 23 was opened and the reactionliquid was transferred to a storage tank 203 via line 23.

Step (1-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

A reaction was carried out using an apparatus like that shown in FIG. 3.

A thin film distillation apparatus 301 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.1 m² was heated to220° C., and an internal pressure was set to about 13 kPa. The mixturerecovered in storage tank 203 in step (1-2) was heated to 150° C. andsupplied to the top of the thin film distillation apparatus 301 at arate of about 1120 g/hr via a line 31. A liquid phase component wasextracted from a line 32 from the bottom of the thin film distillationapparatus 301 and circulated to the top of the thin film distillationapparatus 301 via a line 36. A gaseous phase component was extractedfrom a line 33 from the thin film distillation apparatus 301 andsupplied to a continuous multistage distillation column 302.

The gaseous phase component extracted via the line 33 from the thin filmdistillation apparatus 301 was continuously fed to an intermediate stageof the continuous multistage distillation column 302 having an innerdiameter of about 5 cm and column length of 2 m and packed with Dixonpacking (diameter: 6 mm) to carry out distillative separation of thegaseous phase component. The amount of heat required for distillativeseparation was supplied by circulating the liquid in the bottom of thecolumn through a line 39 and a reboiler 305. The liquid temperature inthe bottom of the continuous multistage distillation column 302 was 150°C., and the pressure at the top of the column was about 15 kPa. A liquidphase component was extracted from the line 33 of the continuousmultistage distillation column 302 provided at a location lower than aline 32 and supplied to a continuous multistage distillation column 312.The continuous multistage distillation column 312 was a continuousmultistage distillation column having an inner diameter of about 5 cmand column length of 2 m packed with Dixon packing (diameter: 6 mm), andwas used to carry out distillative separation of the liquid phasecomponent extracted from the continuous multistage distillation column302 with this distillation column. The amount of heat required fordistillative separation was supplied by circulating liquid in the bottomof the column through a line 41 and a reboiler 310. The liquidtemperature in the bottom of the multistage continuous distillationcolumn 312 was 170° C., and the pressure at the top of the column wasabout 15 kPa. Gas distilled from the top of the continuous multistagedistillation column 312 was condensed in a condenser 308 via a line 34,continuously extracted from a line 35 at the rate of about 89 g/hr andrecovered in a storage tank 309. Liquid extracted from line was asolution containing about 99.8% by weight of hexamethylene diisocyanate,and the yield based on hexamethylene diamine was about 85%.

Step (1-4) Recovery of Aromatic Hydroxy Compound

An apparatus was used like that shown in FIG. 3.

The liquid phase component recovered in storage tank 307 in step (1-3)was continuously fed to the intermediate stage of a continuousmultistage distillation column 313 having an inner diameter of about 5cm and a column length of 2 m and packed with Dixon packing (diameter: 6mm) to carry out separative distillation of the liquid phase component.The amount of heat required for distillative separation was supplied bycirculating a portion of the liquid in the bottom of the column througha line 45 and a reboiler 315. The liquid temperature of the liquid inthe bottom of continuous multistage distillation column 313 was 260° C.and the pressure at the top of column was about 1.3 kPa. Gas distilledfrom the top of continuous multistage distillation column 313 wascondensed in a condenser 316 via a line 44 and continuously extractedinto a storage tank 316 via a line 46.

A liquid phase component was extracted from a line 48 of the continuousmultistage distillation column 313 provided at a location lower than aline 43 and supplied to a continuous multistage distillation column 318.

The liquid phase component supplied to the continuous multistagedistillation column 318 via the line 48 was separated by distillation inthat distillation column. The liquid temperature at the bottom of thecontinuous multistage distillation column 318 was 240° C. and thepressure at the top of the column was about 0.5 kPa. Gas distilled fromthe top of the distillation column 318 was condensed in a condenser 319via a line 49 and continuously extracted at a rate of about 180 g/hrinto a storage tank 309 via a line 50.

Liquid extracted from line 46 was a solution containing about 99% byweight of 4-t-octylphenol. In addition, liquid extracted from line 50was a liquid containing about 99% by weight of bisphenol A.

Example 2

Step (2-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 14.1 kg of 2,4-di-t-amylphenol(Tokyo Chemical Industry Co., Ltd., Japan) instead of 4-t-octylphenol,and using 8.64 kg of bisphenol A polycarbonate.

Step (2-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (2-1) at 9.08 kg/hrinstead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at 0.46 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (2-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (2-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 150° C. and at a rate of about 1165 g/hr, condensinggas distilled from the top of the continuous multistage distillationcolumn 312 in condenser 308 via line 34, continuously extracting fromline 35 at a rate of about 69 g/hr and recovering in storage tank 309.The liquid extracted from a line 35 was a solution containing 99.8% byweight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 85%.

Step (2-4): Recovery of Aromatic Hydroxy Compound

An apparatus was used like that shown in FIG. 3.

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (2-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), a solution containing about 99% by weight of2,4-di-t-amylphenol was recovered from a line 46 at a rate of about 640g/hr, and a liquid containing about 99% by weight of bisphenol A wasrecovered from line 50 at the rate of about 370 g/hr.

Example 3

Step (3-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 13.2 kg of 4-nonylphenol (AldrichCorp., USA) instead of 4-t-octylphenol, and using 8.64 kg of bisphenol Apolycarbonate.

Step (3-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (3-1) at a rate of10.9 kg/hr instead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at a rate of 0.58 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (3-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (3-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 150° C. and at a rate of 1.2 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 73 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing 99.8% byweight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 84%.

Step (3-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (3-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), a solution containing about 99% by weight of 4-nonylphenolwas recovered from line 46 at the rate of about 630 g/hr, and a liquidcontaining about 99% by weight of bisphenol A was recovered from line 50at a rate of about 382 g/hr.

Example 4

Step (4-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 24.3 kg of 4-dodecylphenol(Aldrich Corp., USA) instead of 4-t-octylphenol, and using 10.7 kg ofbisphenol A polycarbonate.

Step (4-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (4-1) at 17.5 kg/hrinstead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at 0.62 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (4-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (4-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 150° C. and at a rate of 2.0 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 83 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 85%.

Step (4-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (4-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), a solution containing about 99% by weight of 4-dodecylphenolwas recovered from a line 46 at the rate of about 1250 g/hr, and aliquid containing about 99% by weight of bisphenol A was recovered froma line 50 at a rate of about 445 g/hr.

Example 5

Step (5-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 11.3 kg of 4-cumylphenol (AldrichCorp., USA) instead of 4-t-octylphenol, and using 7.7 kg of bisphenol Apolycarbonate.

Step (5-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (5-1) at 9.50 kg/hrinstead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at 0.50 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (5-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (5-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 150° C. and at a rate of 2.1 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 125 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 83%.

Step (5-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (5-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), a solution containing about 99% by weight of 4-cumylphenolwas recovered from line 46 at a rate of about 1110 g/hr, and a liquidcontaining about 99% by weight of bisphenol A was recovered from line 50at a rate of about 660 g/hr.

Example 6

Step (6-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 18.2 kg of 2,4-dicumylphenol(Aldrich Corp., USA) instead of 4-t-octylphenol, and using 6.34 kg ofbisphenol A polycarbonate.

Step (6-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (6-1) at 12.3 kg/hrinstead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at 0.51 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (6-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (6-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 150° C. and at a rate of 2.1 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 100 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 82%.

Step (6-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (6-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), a solution containing about 99% by weight of2,4-dicumylphenol was recovered from a line 46 at a rate of about 1410g/hr, and a liquid containing about 99% by weight of bisphenol A wasrecovered from line 50 at the rate of about 510 g/hr.

Example 7

Step (7-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 16.8 kg of 2,4-di-t-amylphenol(Aldrich Corp., USA) instead of 4-t-octylphenol, using 6.91 kg ofbisphenol A polycarbonate, and mixing 0.10 kg of titaniumtetra-isopropoxide (Aldrich Corp., USA) into the 2,4-di-t-amylphenol.

Step (7-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (7-1) at 11.9 kg/hrinstead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at 0.46 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (7-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (7-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 150° C. and at a rate of 1.98 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 86 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 80%.

Step (7-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (7-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), a solution containing about 99% by weight of2,4-di-t-amylphenol was recovered from a line 46 at a rate of about 1203g/hr, and a liquid containing about 99% by weight of bisphenol A wasrecovered from a line 50 at a rate of about 430 g/hr.

Example 8

Step (8-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 15.6 kg of bisphenol A (AldrichCorp., USA) instead of 4-t-octylphenol, and using 6.57 kg of bisphenol Apolycarbonate.

Step (8-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (8-1) at 11.3 kg/hrinstead of the mixture produced in step (1-1) and supplyinghexamethylene diamine at 0.44 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (8-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (8-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 180° C. and at a rate of 2.12 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 90 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 77%.

Step (8-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (8-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from a line 50 at a rate of about 1633 g/hr.

Example 9

Step (9-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 25.3 kg of 2,4-di-t-amylphenolinstead of 4-t-octylphenol, and using 10.4 kg of bisphenol Apolycarbonate.

Step (9-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (9-1) at 8.92 kg/hrinstead of the mixture produced in step (1-1) and supplying3-aminomethyl-3,5,5-trimethyl cyclohexylamine at 0.51 kg/hr to thereactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 3-aminomethyl-3,5,5-trimethyl cyclohexylamine was notdetected.

Step (9-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (9-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 180° C. and at a rate of 2.10 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 119 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of isophorone diisocyanate, and the yield based on3-aminomethyl-3,5,5-trimethyl cyclohexylamine was about 80%.

Step (9-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (9-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from a line 50 at a rate of about 500 g/hr.

Example 10

Step (10-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

Waste compact disks (polycarbonate vapor-deposited with aluminum andcoated with lacquer) were crushed with a shredder to a particle diameterof about 1 to 15 mm.

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 33.8 kg of 2,4-di-t-amylphenolinstead of 4-t-octylphenol, and using 13.8 kg of the polycarbonatecrushed according to the method described above instead of bisphenol Apolycarbonate.

Step (10-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (10-1) at 11.9 kg/hrinstead of the mixture produced in step (1-1) and supplying3-aminomethyl-3,5,5-trimethyl cyclohexylamine at 0.68 kg/hr to thereactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 3-aminomethyl-3,5,5-trimethyl cyclohexylamine was notdetected.

Step (10-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (10-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 175° C. and at a rate of 1.90 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 90 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of isophorone diisocyanate, and the yield based on3-aminomethyl-3,5,5-trimethyl cyclohexylamine was about 67%.

Step (10-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (10-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from line 50 at the rate of about 390 g/hr.

Example 11

Step (11-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 33.3 kg of 2,4,-di-cumylphenolinstead of 4-t-octylphenol, and using 9.8 kg of bisphenol Apolycarbonate.

Step (11-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (11-1) at 10.7 kg/hrinstead of the mixture produced in step (1-1) and supplying3-aminomethyl-3,5,5-trimethyl cyclohexylamine at 0.47 kg/hr to thereactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 3-aminomethyl-3,5,5-trimethyl cyclohexylamine was notdetected.

Step (11-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (11-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 180° C. and at a rate of 2.20 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 94 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of isophorone diisocyanate, and the yield based on3-aminomethyl-3,5,5-trimethyl cyclohexylamine was about 77%.

Step (11-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (11-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from a line 50 at the rate of about 395 g/hr.

Example 12

Step (12-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 25.5 kg of bisphenol A instead of4-t-octylphenol, and using 10.7 kg of bisphenol A polycarbonate.

Step (12-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (12-1) at 9.04 kg/hrinstead of the mixture produced in step (1-1) and supplying3-aminomethyl-3,5,5-trimethyl cyclohexylamine at 0.53 kg/hr to thereactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 3-aminomethyl-3,5,5-trimethyl cyclohexylamine was notdetected.

Step (12-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (12-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 180° C. and at a rate of 1.89 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 99 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of isophorone diisocyanate, and the yield based on3-aminomethyl-3,5,5-trimethyl cyclohexylamine was about 72%.

Step (12-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (12-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from a line 50 at the rate of about 420 g/hr.

Example 13

Step (13-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 34.1 kg of 4-t-octylphenol andusing 11.1 kg of bisphenol A polycarbonate.

Step (13-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (13-1) at 11.3 kg/hrinstead of the mixture produced in step (1-1) and supplying4,4′-methylenebis(cyclohexylamine) (Aldrich Corp., USA) at 0.63 kg/hr tothe reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 4,4′-methylenebis(cyclohexylamine) was not detected.

Step (13-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The reaction was carried out using an apparatus like that shown in FIG.4. A thin film distillation apparatus 401 (Kobelco Eco-Solutions Co.,Ltd., Japan) having a heat-conducting surface area of 0.1 m² was heatedto 280° C., and the internal pressure was set to about 0.5 kPa. Themixture recovered in storage tank 203 in step (13-2) was heated to 180°C. and supplied to the top of the thin film distillation apparatus 401at a rate of about 2210 g/hr via a line 61. A portion of a liquid phasecomponent extracted from the bottom of the thin film distillationapparatus 401 was circulated to the top of the thin film distillationapparatus 401 via a line 66 and a line 60, while the remainder wasextracted into a storage tank 407. On the other hand, a gaseous phasecomponent was extracted from a line 62 and supplied to a continuousmultistage distillation column 402.

The gaseous phase component extracted via the line 62 from the thin filmdistillation apparatus 401 was continuously fed to the intermediatestage of the continuous multistage distillation column 402 having aninner diameter of about 5 cm and a column length of 2 m and packed withDixon packing (diameter: 6 mm) to carry out distillative separation ofthe gaseous phase component. The amount of heat required fordistillative separation was supplied by circulating the liquid in thebottom of the column through a line 69 and a reboiler 405. The liquidtemperature in the bottom of the continuous multistage distillationcolumn 402 was 220° C., and the pressure at the top of the column wasabout 3 kPa. A liquid phase component was supplied from the bottom ofthe continuous multistage distillation column 402 to a continuousmultistage distillation column 412 via the line 69 and the line 63. Thecontinuous multistage distillation column 412 was a continuousmultistage distillation column having an inner diameter of about 5 cmand a column length of 2 m and packed with Dixon packing (diameter: 6mm), and distillative separation of the liquid phase component suppliedfrom the continuous multistage distillation column 402 was carried outwith this distillation column. The amount of heat required fordistillative separation was supplied by circulating liquid in the bottomof the column through a line 71 and a reboiler 410. The liquidtemperature in the bottom of the multistage continuous distillationcolumn 412 was 230° C., and the pressure at the top of the column wasabout 0.5 kPa. Gas distilled from the top of the continuous multistagedistillation column 412 was condensed in a condenser 408 via a line 64,continuously extracted from a line 65 at a rate of about 105 g/hr andrecovered in a storage tank 409.

Liquid extracted from the line 65 was a solution containing about 99% byweight of 4,4′-methylenebis(cyclohexylisocyanate), and the yield basedon 4,4′-methylenebis(cyclohexylamine) was about 72%.

Step (13-4) Recovery of Aromatic Hydroxy Compound

Next, an apparatus was used like that shown in FIG. 4.

The liquid phase component recovered in storage tank 407 in step (13-3)was continuously fed to an intermediate stage of a continuous multistagedistillation column 413 having an inner diameter of about 5 cm and acolumn length of 2 m and packed with Dixon packing (diameter: 6 mm) tocarry out separative distillation of the liquid phase component. Theamount of heat required for distillative separation was supplied bycirculating a portion of the liquid in the bottom of the column througha line 75 and a reboiler 415. The liquid temperature of the liquid inthe bottom of continuous multistage distillation column 413 was 170° C.and the pressure at the top of column was about 1.3 kPa. Gas distilledfrom the top of continuous multistage distillation column 413 wascondensed in a condenser 414 via a line 74 and continuously extractedinto a storage tank 416 via a line 76. A liquid phase component wasextracted from a line 78 of the continuous multistage distillationcolumn 413 provided at a location lower than a line 73 and supplied to acontinuous multistage distillation column 418.

The liquid phase component supplied to the continuous multistagedistillation column 418 via the line 78 was separated by distillation inthat distillation column. The liquid temperature at the bottom of thecontinuous multistage distillation column 418 was 240° C. and thepressure at the top of the column was 0.5 kPa. Gas distilled from thetop of the distillation column 418 was condensed in a condenser 419 viaa line 79 and continuously extracted at a rate of about 350 g/hr into astorage tank 409 via a line 80. Liquid extracted from the line 80 was asolution containing about 99% by weight of bisphenol A.

Example 14

Step (14-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 25.3 kg of 2,4-di-t-amylphenolinstead of 4-t-octylphenol and using 10.4 kg of bisphenol Apolycarbonate.

Step (14-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (14-1) at 8.92 kg/hrinstead of the mixture produced in step (1-1) and supplying4,4′-methylenebis(cyclohexylamine) at 0.63 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 4,4′-methylenebis(cyclohexylamine) was not detected.

Step (14-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (13-3) of Example 13 was carried out with theexception of supplying the mixture recovered in step (14-2) instead ofthe mixture recovered in step (13-2) to the thin film distillationapparatus 401 at 180° C. and at a rate of 2.28 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column412 in condenser 408 via a line 64, continuously extracting from a line65 at a rate of about 132 g/hr and recovering in storage tank 409. Theliquid extracted from the line 65 was a solution containing about 99.8%by weight of 4,4′-methylenebis(cyclohexylisocyanate), and the yieldbased on 4,4′-methylenebis(cyclohexylamine) was about 70%.

Step (14-4): Recovery of Aromatic Hydroxy Compound

The same method as step (13-4) of Example 13 was carried out with theexception of using the liquid phase component recovered in step (14-3)instead of the liquid phase component recovered in storage tank 407 instep (13-3), and a liquid containing about 99% by weight of bisphenol Awas recovered from line 80 at a rate of about 433 g/hr.

Example 15

Step (15-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 28.3 kg of 4-dodecylphenol(Aldrich Corp., USA) instead of 4-t-octylphenol, and using 10.4 kg ofbisphenol A polycarbonate.

Step (15-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (15-1) at 9.67 kg/hrinstead of the mixture produced in step (1-1) and supplying2,4-toluenediamine (Aldrich Corp., USA) at 0.37 kg/hr to the reactor202.

As a result of analyzing the solution following the reaction by gaschromatography, 2,4-toluenediamine was not detected.

Step (15-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (15-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 160° C. and at a rate of 1.75 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 73 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of 2,4-tolylenediisocyanate, and the yield based on2,4-toluenediamine was about 79%.

Step (15-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (15-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from line 50 at a rate of about 380 g/hr.

Example 16

Step (16-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 29.5 kg of 2,4-di-t-amylphenolinstead of 4-t-octylphenol, and using 12.1 kg of bisphenol Apolycarbonate.

Step (16-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (16-1) at 10.4 kg/hrinstead of the mixture produced in step (1-1) and supplying2,4-toluenediamine at 0.43 kg/hr to the reactor 202. As a result ofanalyzing the solution following the reaction by gas chromatography,2,4-toluenediamine was not detected.

Step (16-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (16-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 160° C. and at a rate of 1.97 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 86 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of 2,4-tolylenediisocyanate, and the yield based on2,4-toluenediamine was about 78%.

Step (16-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (16-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from line 50 at a rate of about 460 g/hr.

Example 17

Step (17-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 24.4 kg of 2-phenylphenol (WakoPure Chemical Industries, Ltd., Japan) instead of 4-t-octylphenol, andusing 12.9 kg of bisphenol A polycarbonate.

Step (17-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (17-1) at 9.35 kg/hrinstead of the mixture produced in step (1-1) and supplying2,4-toluenediamine at 0.34 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 2,4-toluenediamine was not detected.

Step (17-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (17-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 250° C. and at a rate of 2.12 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 82 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of 2,4-tolylenediisocyanate, and the yield based on2,4-toluenediamine was about 76%.

Step (17-4): Recovery of Aromatic Hydroxy Compound

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (17-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a solution containing about 99% by weight of bisphenol Awas recovered from a line 50 at the rate of about 440 g/hr.

Example 18

Step (18-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 24.4 kg of 4-nonylphenol insteadof 4-t-octylphenol, and using 9.68 kg of bisphenol A polycarbonate.

Step (18-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (18-1) at 8.53 kg/hrinstead of the mixture produced in step (1-1) and supplying4,4′-methylenedianiline at 0.59 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 4,4′-methylenedianiline was not detected.

Step (18-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (13-3) of Example 13 was carried out with theexception of supplying the mixture recovered in step (18-2) instead ofthe mixture recovered in step (13-2) to the thin film distillationapparatus 401 at 180° C. and at a rate of 2.10 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column412 in condenser 408 via a line 64, continuously extracting from a line65 at a rate of about 107 g/hr and recovering in storage tank 409. Theliquid extracted from the line 65 was a solution containing about 99.8%by weight of 4,4′-diphenylmethane diisocyanate, and the yield based on4,4′-methylenedianiline was about 63%.

Step (18-4): Recovery of Aromatic Hydroxy Compound

The same method as step (13-4) of Example 13 was carried out with theexception of using the liquid phase component recovered in step (18-3)instead of the liquid phase component recovered in storage tank 407 instep (13-3), and a solution containing about 99% by weight of bisphenolA was recovered from a line 80 at a rate of about 410 g/hr.

Example 19

Step (19-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 25.3 kg of 2,4-di-t-amylphenolinstead of 4-t-octylphenol, and using 10.4 kg of bisphenol Apolycarbonate.

Step (19-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (19-1) at 8.92 kg/hrinstead of the mixture produced in step (1-1) and supplying4,4′-methylenedianiline at 0.59 kg/hr to the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 4,4′-methylenedianiline was not detected.

Step (19-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (13-3) of Example 13 was carried out with theexception of supplying the mixture recovered in step (19-2) instead ofthe mixture recovered in step (13-2) to the thin film distillationapparatus 401 at 180° C. and at a rate of 1.98 kg/hr, condensing gasdistilled from the top of the continuous multistage distillation column412 in condenser 408 via a line 64, continuously extracting from a line65 at a rate of about 104 g/hr and recovering in storage tank 409. Theliquid extracted from the line 65 was a solution containing about 99.8%by weight of 4,4′-diphenylmethane diisocyanate, and the yield based on4,4′-methylenedianiline was about 66%.

Step (19-4): Recovery of Aromatic Hydroxy Compound

The same method as step (13-4) of Example 13 was carried out with theexception of using the liquid phase component recovered in step (19-3)instead of the liquid phase component recovered in storage tank 407 instep (13-3), and a solution containing about 99% by weight of bisphenolA was recovered from a line 80 at a rate of about 397 g/hr.

Example 20

Step (20-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 29.5 kg of 4-t-octylphenol and11.8 kg of bisphenol A polycarbonate.

Step (20-2): Production of Carbamic Acid Ester

The same method as step (1-2) of Example 1 was carried out with theexception of supplying the mixture prepared in step (20-1) at 10.3 kg/hrinstead of the mixture produced in step (1-1) and supplying4,4′-methylenedianiline at 0.62 kg/hr instead of hexamethylene diamineto the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, 4,4′-methylenedianiline was not detected.

Step (20-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The reaction was carried out using an apparatus like that shown in FIG.5.

A thin film distillation apparatus 501 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.1 m² was heated to200° C., and the internal pressure was set to about 13 kPa. The mixturerecovered in storage tank 203 in step (20-2) was heated to 180° C. andsupplied to the top of the thin film distillation apparatus 501 at arate of about 2200 g/hr via a line A1. A portion of a liquid phasecomponent extracted from the bottom of the thin film distillationapparatus 501 was circulated to the top of the thin film distillationapparatus 501 via a line A3 and a line A4. On the other hand, a gaseousphase component was extracted from a line A2. In addition, the liquidphase component not circulated to the thin film distillation apparatus501 was extracted into a storage tank 507.

The gaseous phase component extracted via the line A2 from the thin filmdistillation apparatus 501 was continuously fed to the intermediatestage of a continuous multistage distillation column 502 having an innerdiameter of about 5 cm and a column length of 2 m and packed with Dixonpacking (diameter: 6 mm) to carry out distillative separation of thegaseous phase component. The amount of heat required for distillativeseparation was supplied by circulating the liquid in the bottom of thecolumn through a line A7 and a reboiler 505. The liquid temperature inthe bottom of the continuous multistage distillation column 502 was 230°C., and the pressure at the top of the column was about 1.3 kPa. Agaseous phase component of the gas distilled from the top of thecontinuous multistage distillation column 502 was extracted via a lineA5, and after condensing in a condenser 503, was continuously extractedinto a storage tank 504 via a line A6. The solution obtained in storagetank 504 contained about 99% by weight of 4-t-octylphenol.

The liquid phase component extracted into storage tank 507 was suppliedto a continuous multistage distillation column 508 via a line A10. Thecontinuous multistage distillation column 508 was a continuousmultistage distillation column having an inner diameter of about 5 cmand a column length of 2 m and packed with Dixon packing (diameter: 6mm), and distillative separation of the liquid phase component suppliedfrom storage tank 507 was carried out with this distillation column. Theamount of heat required for distillative separation was supplied bycirculating liquid in the bottom of the column through a line A13 and areboiler 511. The liquid temperature in the bottom of the multistagecontinuous distillation column 508 was 210° C., and the pressure at thetop of the column was about 0.5 kPa. A liquid phase component wasextracted from a line A15 of the continuous multistage distillationcolumn 508 provided at a location lower than a line A10 and supplied toa continuous multistage distillation column 513. The continuousmultistage distillation column 513 was a continuous multistagedistillation column having an inner diameter of about 5 cm and columnlength of 2 m and packed with Dixon packing (diameter: 6 mm), anddistillative separation of the liquid phase component extracted from thecontinuous multistage distillation column 508 was carried out with thisdistillation column. Gas distilled from the top of the continuousmultistage distillation column 513 was condensed in a condenser 514 viaa line A17 and continuously extracted from a line A18 at a rate of about81 g/hr and recovered in a storage tank 515.

Liquid extracted from the line A18 was a solution containing about 99%by weight of 4,4′-diphenylmethane diisocyanate, and the yield based on4,4′-methylenedianiline was about 52%.

Step (20-4) Recovery of Aromatic Hydroxy Compound

An apparatus was used like that shown in FIG. 6.

The liquid phase component recovered in storage tank 512 in step (20-3)was continuously fed through a line B1 to an intermediate stage of acontinuous multistage distillation column 601 having an inner diameterof about 5 cm and a column length of 2 m and packed with Dixon packing(diameter: 6 mm) to carry out separative distillation of the liquidphase component. The amount of heat required for distillative separationwas supplied by circulating a portion of the liquid in the bottom of thecolumn through a line B3 and a reboiler 604. The liquid temperature ofthe liquid in the bottom of continuous multistage distillation column601 was 200° C. and the pressure at the top of column was about 5.8 kPa.A liquid phase component was extracted from a line B7 of the continuousmultistage distillation column 601 provided at a location lower than theline B1, and supplied to a continuous multistage distillation column 606from line B7.

The liquid phase component supplied to the continuous multistagedistillation column 606 was separated by distillation with thisdistillation column. The liquid temperature of the liquid in the bottomof continuous multistage distillation column 606 was 240° C. and thepressure at the top of column was 0.5 kPa. Gas distilled from the top ofcontinuous multistage distillation column 606 was condensed in acondenser 607 via a line B8 and continuously extracted into a storagetank 608 via a line B9 at a rate of about 310 g/hr. Liquid extractedfrom line B9 was a solution containing about 99% by weight of bisphenolA.

Example 21

Step (21-1): Preparation of Mixture of Aromatic Polycarbonate andMethylene Chloride Solution

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 9.36 kg of methylene chloride(Wako Pure Chemical Industries, Ltd., Japan) instead of 4-t-octylphenol,using 7.26 kg of bisphenol A polycarbonate, and holding at 30° C. in thereactor 102.

Step (21-2): Production of Carbamic Acid Ester

The reactor 202 was maintained at 35° C., and the same method as step(1-2) of Example 1 was carried out with the exception of supplying themixture prepared in step (21-1) at 4.15 kg/hr instead of the mixtureproduced in step (1-1) and supplying hexamethylene diamine at 0.24 kg/hrto the reactor 202.

As a result of analyzing the solution following the reaction by gaschromatography, hexamethylene diamine was not detected.

Step (21-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

The same method as step (1-3) of Example 1 was carried out with theexception of supplying the mixture recovered in step (21-2) instead ofthe mixture recovered in step (1-2) to the thin film distillationapparatus 301 at 35° C. and at a rate of 1660 g/hr, condensing gasdistilled from the top of the continuous multistage distillation column312 in condenser 308 via a line 34, continuously extracting from a line35 at a rate of about 111 g/hr and recovering in storage tank 309. Theliquid extracted from the line 35 was a solution containing about 99.8%by weight of hexamethylene diisocyanate, and the yield based onhexamethylene diamine was about 82%.

Step (21-4): Recovery of Aromatic Hydroxy Compound

An apparatus was used like that shown in FIG. 4.

The same method as step (1-4) of Example 1 was carried out with theexception of using the liquid phase component recovered in step (21-3)instead of the liquid phase component recovered in storage tank 307 instep (1-3), and a liquid containing about 99% by weight of bisphenolAwas recovered from a line 50 at a rate of about 358 g/hr.

Example 22

Step (22-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared by carrying out the same method as step (1-1) ofExample 1 with the exception of using 14.0 kg of 4-t-octylphenol andusing 10.3 kg of bisphenol A polycarbonate.

Step (22-2): Production of Carbamic Acid Ester

A reaction was carried out using an apparatus like that shown in FIG. 7.

The mixture prepared in step (22-1) was supplied from a storage tank 701to a baffled SUS reactor 703 at a rate of about 6.09 kg/hr via a line C1with a line C3 closed, and hexamethylene diamine was supplied from astorage tank 702 to the reactor 703 via a line C2 at a rate of about0.37 kg/hr.

As a result of analyzing the solution following the reaction by liquidchromatography, hexamethylene diamine was not detected.

Step (22-3): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

Subsequently, a reaction was carried out using an apparatus like thatshown in FIG. 7.

The SUS reactor 703 was heated to 220° C. and the pressure inside thereactor was reduced to 1.3 kPa. A gaseous phase component was extractedfrom a line C3, and the gaseous phase component was continuously fed toan intermediate stage of a continuous multistage distillation column 704having an inner diameter of about 5 cm and a column length of 2 m andpacked with Dixon packing (diameter: 6 mm) to carry out distillativeseparation. The amount of heat required for distillative separation wassupplied by circulating the liquid in the bottom of the column via aline C6 and a reboiler 706. The liquid temperature at the bottom of thecontinuous multistage distillation column 704 was 150° C. and thepressure at the top of the column was about 15 kPa. Gas distilled fromthe top of the continuous multistage distillation column 704 wascondensed in a condenser 705 via a line C4 and continuously extractedfrom a line C5 at a rate of about 363 g/hr. The solution extracted fromthe line C5 was a solution containing about 99% by weight ofhexamethylene diisocyanate, and the yield based on hexamethylene diaminewas about 67%.

Step (22-4): Recovery of Aromatic Hydroxy Compound

The liquid phase component in step (22-3) was supplied from the bottomof the reactor 703 to a continuous multistage distillation column 707via a line C18. The distillation column 707 was a continuous multistagedistillation column having an inner diameter of about 5 cm and a columnlength of 2 m and packed with Dixon packing (diameter: 6 mm), anddistillative separation of the liquid phase component was carried outwith this distillation column. The amount of heat required fordistillative separation was supplied by circulating the liquid in thebottom of the column via a line C11 and a reboiler 709. The liquidtemperature at the bottom of the continuous multistage distillationcolumn 707 was 200° C. and the pressure at the top of the column wasabout 1.5 kPa. Gas distilled from the top of the continuous multistagedistillation column 707 was condensed in a condenser 708 via a line C9and continuously extracted into a storage tank 714 via a line C10. Thecompound recovered in the storage tank 714 was 4-t-octylphenol. On theother hand, a portion of the liquid phase component of the continuousmultistage distillation column 707 was supplied to a continuousmultistage distillation column 710 from a line C11 via a line C13. Thedistillation column 710 was a continuous multistage distillation columnhaving an inner diameter of about 5 cm and a column length of 2 m andpacked with Dixon packing (diameter: 6 mm), and distillative separationof the liquid phase component was carried out with this distillationcolumn. The amount of heat required for distillative separation wassupplied by circulating liquid in the bottom of the column via a lineC16 and reboiler 713. The liquid temperature at the bottom of thecontinuous multistage distillation column 710 was 250° C. and thepressure at the top of the column was about 0.5 kPa. Gas distilled fromthe top of the continuous multistage distillation column 710 wascondensed in a condenser 711 via a line C14, and continuously extractedinto a storage tank 715 via a line C15. The compound recovered in thestorage tank 715 was bisphenol A.

Example 23

Step (23-1): Production of Carbamic Acid Ester Compound

134.2 g of poly(bisphenol A carbonate) (Aldrich Corp., USA, weightaverage molecular weight: 64,000 (catalog value)) and 280 g of methylenechloride were placed in a reaction vessel in the form of a 1000 mLvolumetric four-mouth flask to which was attached a Dimroth condenser,dropping funnel and three-way valve followed by stirring to prepare asolution. A mixture of 11.6 g (0.10 mol) of hexamethylene diamine and 30g of methylene chloride were placed in the dropping funnel and theinside of the reaction vessel was replaced with nitrogen. The reactionvessel was immersed in a water bath adjusted to 10° C. and a mixture ofhexamethylene diamine and chloroform were dropped into the reactionvessel over the course of about 1 hour. Following completion ofdropping, the mixture was stirred for about 4 hours. When a portion ofthe resulting mixed solution was sampled and subjected to ¹H— and¹³C-NMR analyses, the product was confirmed to be a carbamic acid estercompound as shown FIG. 8 and FIG. 9.

Step (23-2): Production of Isocyanate by Thermal Decomposition ofCarbamic Acid Ester

A vacuum pump and a vacuum controller were attached to a moleculardistillation apparatus (Model MS-300, Sibata Scientific Technology Ltd.,Japan) having a jacketed heating unit using oil circulation, and thepurge line of the vacuum controller was connected to a nitrogen gasline. The inside of the molecular distillation apparatus was replacedwith nitrogen and the heating unit was heated to 200° C. A solution wasthen prepared by mixing 405 g of the mixture containing carbamic acidester compound obtained in Example 1 and 120 g of benzyl butyl phthalate(guaranteed reagent, Wako Pure Chemical Industries, Ltd., Japan). Theinside of the molecular distillation apparatus was reduced to 1.3 kPa,and the slurry was charged into the molecular distillation apparatus ata rate of about 5 g/min while rotating the wiper of the moleculardistillation apparatus at about 300 rpm to thermally decompose thepolycarbamic acid ester compound. 12.1 g of a thermal decompositionproduct were obtained in the sample receiver. As a result of analysis,chloroform was recovered in the low boiling point trap, a mixturecontaining bisphenol A and benzyl butyl phthalate were recovered in thefeedback receiver, and the liquid obtained in the sample receivercontained about 95% hexamethylene diisocyanate, and the yield based onhexamethylene diamine was 70%.

Step (23-3): Recovery of Aromatic Hydroxy Compound

The mixture containing bisphenol A and benzyl butyl phthalate obtainedin the feedback receiver in step (23-2) was heated to 280° C. andcharged into a molecular distillation apparatus (Model MS-300, ShibataScientific Technology Ltd., Japan) at a rate of about 10 g/min afterreducing the pressure inside the apparatus to 0.13 kPa followed bydistilling off the benzyl butyl phthalate. About 200 mL of toluene werethen added to the resulting liquid phase component while heating, andafter filtering out the precipitating component, the toluene solutionwas allowed to stand undisturbed until it reached room temperature. Theprecipitated crystals were filtered out, and when a portion of thecrystals were sampled and subjected to ¹H— and ¹³C-NMR analysis, thecrystals were found to contain about 99% by weight of bisphenol A.

Comparative Example 1

Step (A-1): Preparation of Mixture of Aromatic Polycarbonate andAromatic Hydroxy Compound

A mixture was prepared using an apparatus like that shown in FIG. 1.

11.1 kg of molten 4-t-octylphenol were transferred from storage tank 101to storage tank 102 heated to 250° C. after replacing the inside of thetank with nitrogen with a line 12 closed. 5.19 kg of bisphenol Apolycarbonate (Aldrich Corp. USA, weight average molecular weight:65,000) were charged from a hopper 100 into the reactor 102 and stirred.After confirming that the bisphenol A polycarbonate had dissolved, line12 was opened and the mixture was transferred to storage tank 103.

Step (A-2): Reaction of Aromatic Polycarbonate and Amine Compound

A reaction was carried out using an apparatus like that shown in FIG. 2.

The mixture produced in step (A-1) was supplied from storage tank 103via a line 21 to baffled SUS reactor 202 held at about 150° afterreplacing the inside of the reactor with nitrogen at a rate of 4.08kg/hr with a line 23 closed. Tributylamine (Aldrich Corp., USA) wassupplied from storage tank 201 via a line 22 to the reactor 202 at arate of about 0.33 kg/hr. One hour after the start of addition, the line23 was opened and the reaction liquid was transferred to storage tank203 via the line 23.

Step (A-3): Recovery of Amine Compound

An apparatus was used like that shown in FIG. 3.

Thin film distillation apparatus 301 (Kobelco Eco-Solutions Co., Ltd.,Japan) having a heat-conducting surface area of 0.1 m² was heated to220° C., and an internal pressure was set to about 13 kPa. The mixturerecovered in storage tank 203 in step (A-2) was heated to 150° C. andsupplied to the top of the thin film distillation apparatus 301 at arate of about 1500 g/hr via a line 31. A liquid phase component wasextracted from a line 32 from the bottom of the thin film distillationapparatus 301 and circulated to the top of the thin film distillationapparatus 301 via a line 36. The liquid phase component not circulatedto the thin film distillation apparatus 301 was recovered in storagetank 307. A gaseous phase component was extracted from a line 33 fromthe thin film distillation apparatus 301 and supplied to continuousmultistage distillation column 302.

The gaseous phase component extracted via the line 33 from the thin filmdistillation apparatus 301 was continuously fed to an intermediate stageof the continuous multistage distillation column 302 having an innerdiameter of about 5 cm and a column length of 2 m and packed with Dixonpacking (diameter: 6 mm) to carry out distillative separation of thegaseous phase component. The amount of heat required for distillativeseparation was supplied by circulating the liquid in the bottom of thecolumn through a line 39 and a reboiler 305. The liquid temperature inthe bottom of the continuous multistage distillation column 302 was 150°C., and the pressure at the top of the column was about 2.6 kPa. Gasdistilled from the top of the continuous multistage distillation column302 was condensed in a condenser 303 via a line 37, continuouslyextracted from a line 38 and recovered in storage tank 304. The liquidextracted from the line 38 was tributylamine.

Step (A-4) Recovery of Aromatic Hydroxy Compound

An apparatus was used like that shown in FIG. 3.

The liquid phase component recovered in storage tank 307 in step (A-3)was continuously fed to an intermediate stage of a continuous multistagedistillation column 313 having an inner diameter of about 5 cm and acolumn length of 2 m and packed with Dixon packing (diameter: 6 mm) tocarry out separative distillation of the liquid phase component. Theamount of heat required for distillative separation was supplied bycirculating a portion of the liquid in the bottom of the column througha line 45 and a reboiler 315. The liquid temperature of the liquid inthe bottom of continuous multistage distillation column 315 was 180° C.and the pressure at the top of column was about 1.3 kPa. Gas distilledfrom the top of continuous multistage distillation column 315 wascondensed in a condenser 314 via a line 44 and continuously extractedinto a storage tank 316 via a line 46.

A liquid phase component was extracted from a line 48 of the continuousmultistage distillation column 313 provided at a location lower than aline 43 and supplied to continuous multistage distillation column 318.

The liquid phase component supplied to the continuous multistagedistillation column 318 via the line 48 was separated by distillation inthat distillation column. The liquid temperature at the bottom of thecontinuous multistage distillation column 318 was 240° C. and thepressure at the top of the column was 0.5 kPa. Gas distilled from thetop of the distillation column 318 was condensed in a condenser 319 viaa line 49 and continuously extracted at a rate of about 50 g/hr intostorage tank 309 via a line 50.

Liquid extracted from the line 46 was a solution containing about 99% byweight of 4-t-octylphenol. In addition, liquid extracted from the line50 was a liquid containing about 99% by weight of bisphenol A.

The present application is based on Japanese patent applications filedon Nov. 19, 2007 (Japanese Patent Application Nos. 2007-299497,2007-299504 and 2007-299703), the contents of which are incorporatedherein by reference.

INDUSTRIAL APPLICABILITY

A carbamic acid ester obtained with the process according to the presentembodiment is preferable as a raw material for producing isocyanatewithout using extremely toxic phosgene, and isocyanate obtained with theprocess according to the present embodiment can be preferably used as aproduction raw material of polyurethane foam, paints, adhesives and thelike. In addition, divalent aromatic hydroxy compounds obtained with theprocess according to the present embodiment can be preferably used asproduction raw materials of aromatic polycarbonates. The processaccording to the present embodiment also demonstrates the aspect ofchemical recycling of aromatic polycarbonates. On the basis of theabove, the process according to the present invention is extremelyindustrially useful and has high commercial value.

1. A carbamic acid ester compound represented by the following formula(1):

(wherein R³ represents a group selected from the group consisting ofaliphatic groups having 1 to 20 carbon atoms, each of R⁴ and R⁵independently represents a substituent selected from the grouprepresented by the following formula (2):

and x represents an integer of 0 or more, and each of y and zindependently represents an integer of 1 or more).
 2. The carbamic acidester compound according to claim 1, wherein the R³ represents thealiphatic group, and R⁴ and R⁵ together contain —OH and

or —OH and


3. The carbamic acid ester compound according to claim 1, wherein the R³represents the aliphatic group, and R⁴ and R⁵ contain —OH and


4. The carbamic acid ester compound according to claim 1, wherein the R³represents the aliphatic group, and R⁴ and R⁵ contain —OH and


5. The carbamic acid ester compound according to claim 1, wherein the R³represents —(CH)₆—.
 6. A carbamic acid ester compound compositioncomprising: (i) the carbamic acid ester compound of claim 2, (ii) asecond carbamic acid ester compound represented the following formula(1):

(wherein R³ represents an aliphatic group having 1 to 20 carbon atoms,each of R⁴ and R⁵ represents —OH, and x represents an integer of 0 ormore, and each of y and z independently represents an integer of 1 ormore).
 7. A carbamic acid ester compound composition comprising: (i) thecarbamic acid ester compound of claim 2, (ii) a third carbamic acidester compound represented the following formula (1):

(wherein R³ represents an aliphatic group having 1 to 20 carbon atoms,each of R⁴ and R⁵ represents

and x represents an integer of 0 or more, and each of y and zindependently represents an integer of 1 or more).
 8. A carbamic acidester compound composition comprising: (i) the carbamic acid estercompound of claim 2, (ii) a fourth carbamic acid ester compoundrepresented the following formula (1):

(wherein R³ represents an aliphatic group having 1 to 20 carbon atoms,each of R⁴ and R⁵ represents

x represents an integer of 0 or more, and each of y and z independentlyrepresents an integer of 1 or more).
 9. A carbamic acid ester compoundcomposition comprising: (i) the carbamic acid ester compound of claim 2,(ii) a fifth carbamic acid ester compound represented by the followingformula (1):

(wherein R³ represents an aliphatic group having 1 to 20 carbon atoms,R⁴ and R⁵ together contain

and x represents an integer of 0 or more, and each of y and zindependently represents an integer of 1 or more).
 10. A carbamic acidester compound composition comprising: (i) the carbamic acid estercompound of claim 2, (ii) a second carbamic acid ester compoundrepresented the following formula (1):

(wherein R³ represents an aliphatic group having 1 to 20 carbon atoms,each of R⁴ and R⁵ represents —OH, and x represents an integer of 0 ormore, and each of y and z independently represents an integer of 1 ormore), and (iii) a third carbamic acid ester compound represented by theformula (1) (wherein R³ represents an aliphatic group having 1 to 20carbon atoms, each of R⁴ and R⁵ represents

x represents an integer of 0 or more, and each of y and z independentlyrepresents an integer of 1 or more), (iv) a fourth carbamic acid estercompound represented by the formula (1) (wherein R³ represents analiphatic group having 1 to 20 carbon atoms, each of R⁴ and R⁵represents

x represents an integer of 0 or more, and each of y and z independentlyrepresents an integer of 1 or more) (v) a fifth carbamic acid estercompound represented by the formula (1) (wherein R³ represents analiphatic group having 1 to 20 carbon atoms, R⁴ and R⁵ together contain

and x represents an integer of 0 or more, and each of y and zindependently represents an integer of 1 or more).
 11. The carbamic acidester compound composition according to claim 10, wherein each of the R³in the formula (1) of the carbamic acid ester compound of claim 2 andthe second, third, fourth, and fifth carbamic acid ester compoundsrepresents —(CH)₆—.